Patterning process

ABSTRACT

A pattern is formed by coating a chemically amplified positive resist composition comprising a resin comprising acid labile group-containing recurring units and a photoacid generator onto a substrate, drying to form a resist film, exposing the resist film to high-energy radiation through a phase shift mask including a lattice-like first shifter and a second shifter arrayed on the first shifter and consisting of lines which are thicker than the line width of the first shifter, PEB, developing to form a positive pattern, illuminating or heating the positive pattern to eliminate acid labile groups for increasing alkaline solubility and to induce crosslinking for imparting solvent resistance, coating a reversal film, and dissolving away the positive pattern in an alkaline wet etchant to form a pattern by way of positive/negative reversal.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2009-030281 filed in Japan on Feb. 12, 2009, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a process for forming a pattern by way of positive/negative reversal involving the steps of exposure through a lattice-like pattern mask including lines of different width and development to form a dense and isolated dot positive pattern, acid-generating and heating treatment for converting the positive pattern to be alkali-soluble and solvent-insoluble, coating thereon a reversal film which is slightly alkali soluble, and effecting alkaline development to dissolve away a surface portion of the reversal film and the positive pattern to form a negative pattern. More particularly, it relates to a pattern forming process capable of simultaneously forming dense and isolated holes through a single exposure.

BACKGROUND ART

In the recent drive for higher integration and operating speeds in LSI devices, the pattern rule is made drastically finer. The photolithography which is currently on widespread use in the art is approaching the essential limit of resolution determined by the wavelength of a light source. As the light source used in the lithography for resist pattern formation, g-line (436 nm) or i-line (365 nm) from a mercury lamp was widely used in 1980's. Reducing the wavelength of exposure light was believed effective as the means for further reducing the feature size. For the mass production process of 64 MB dynamic random access memories (DRAM, processing feature size 0.25 μm or less) in 1990's and later ones, the exposure light source of i-line (365 nm) was replaced by a KrF excimer laser having a shorter wavelength of 248 nm. However, for the fabrication of DRAM with a degree of integration of 256 MB and 1 GB or more requiring a finer patterning technology (processing feature size 0.2 μm or less), a shorter wavelength light source was required. Over a decade, photolithography using ArF excimer laser light (193 nm) has been under active investigation. It was expected at the initial that the ArF lithography would be applied to the fabrication of 180-nm node devices. However, the KrF excimer lithography survived to the mass-scale fabrication of 130-nm node devices. So, the full application of ArF lithography started from the 90-nm node. The ArF lithography combined with a lens having an increased numerical aperture (NA) of 0.9 is considered to comply with 65-nm node devices. For the next 45-nm node devices which required an advancement to reduce the wavelength of exposure light, the F₂ lithography of 157 nm wavelength became a candidate. However, for the reasons that the projection lens uses a large amount of expensive CaF₂ single crystal, the scanner thus becomes expensive, hard pellicles are introduced due to the extremely low durability of soft pellicles, the optical system must be accordingly altered, and the etch resistance of resist is low; the postponement of F₂ lithography and the early introduction of ArF immersion lithography were advocated (see Proc. SPIE Vol. 4690, xxix, 2002).

In the ArF immersion lithography, the space between the projection lens and the wafer is filled with water. Since water has a refractive index of 1.44 at 193 nm, pattern formation is possible even using a lens having a numerical aperture (NA) of 1.0 or greater. Theoretically, it is possible to increase the NA to nearly 1.44. It was initially recognized that the resolution could be degraded and the focus be shifted by a variation of water's refractive index with a temperature change. The problem of refractive index variation could be solved by controlling the water temperature within a tolerance of 1/100° C. while it was recognized that the impact of heat from the resist film upon light exposure drew little concern. There was a likelihood that micro-bubbles in water could be transferred to the pattern. It was found that the risk of bubble generation is obviated by thorough deaeration of water and the risk of bubble generation from the resist film upon light exposure is substantially nil. At the initial phase in 1980's of the immersion lithography, a method of immersing an overall stage in water was proposed. Later proposed was a partial-fill method of using a water feed/drain nozzle for introducing water only between the projection lens and the wafer so as to comply with the operation of a high-speed scanner. In principle, the immersion technique using water enabled lens design to a NA of 1 or greater. In optical systems based on traditional refractive index materials, this leads to giant lenses, which would deform by their own weight. For the design of more compact lenses, a catadioptric system was proposed, accelerating the lens design to a NA of 1.0 or greater. A combination of a lens having NA of 1.2 or greater with strong resolution enhancement technology suggests a way to the 45-nm node (see Proc. SPIE Vol. 5040, 724, 2003). Efforts have also been made to develop lenses of NA 1.35.

One candidate for the 32-nm node lithography is lithography using extreme ultraviolet (EUV) radiation with wavelength 13.5 nm. The EUV lithography has many accumulative problems to be overcome, including increased laser output, increased sensitivity, increased resolution and minimized line-width roughness (LWR) of resist coating, defect-free MoSi laminate mask, reduced aberration of reflection mirror, and the like.

The water immersion lithography using a NA 1.35 lens achieves an ultimate resolution of 40 to 38 nm as the half-pitch of a line pattern at the maximum NA, but cannot reach 32 nm. Efforts have been made to develop higher refractive index materials in order to further increase NA. It is the minimum refractive index among projection lens, liquid, and resist film that determines the NA limit of lenses. In the case of water immersion, the refractive index of water is the lowest in comparison with the projection lens (refractive index 1.5 for synthetic quartz) and the resist film (refractive index 1.7 for prior art methacrylate-based film). Thus the NA of projection lens is determined by the refractive index of water. Recent efforts succeeded in developing a highly transparent liquid having a refractive index of 1.65. In this situation, the refractive index of projection lens made of synthetic quartz is the lowest, suggesting a need to develop a projection lens material with a higher refractive index. LuAG (lutetium aluminum garnet Lu₃Al₅O₁₂) having a refractive index of at least 2 is the most promising material, but has the problems of birefringence and noticeable absorption. Even if a projection lens material with a refractive index of 1.8 or greater is developed, the liquid with a refractive index of 1.65 limits the NA to 1.55 at most, failing in resolution of 32 nm despite successful resolution of 35 nm. For resolution of 32 nm, a liquid with a refractive index of 1.8 or greater and resist and protective films with a refractive index of 1.8 or greater are necessary. Among the materials with a refractive index of 1.8 or greater, the high refractive index liquid seems least available. Such a liquid material has not been discovered because a tradeoff between absorption and refractive index is recognized in the art. In the case of alkane compounds, bridged cyclic compounds are preferred to linear ones in order to increase the refractive index, but the cyclic compounds undesirably have too high a viscosity to follow high-speed scanning on the exposure tool stage. Since hafnium oxide particles have high transparency and a refractive index in excess of 2 at 193 nm, it is under study to form a high refractive index liquid by dispersing the particles in water or alkane solvents. However, to increase the refractive index up to 1.8, hafnium oxide must be dispersed in water in an amount of at least 30 wt %. The resulting mixture has a very high viscosity which is incompatible with high-speed scanning. If a liquid with a refractive index of 1.8 is developed, then the component having the lowest refractive index is the resist film, suggesting a need to increase the refractive index of a resist film to 1.8 or higher.

The process that now draws attention under the above-discussed circumstances is a double patterning process involving a first set of exposure and development to form a first pattern and a second set of exposure and development to form a pattern between the first pattern features. See Proc. SPIE Vol. 5754, 1508 (2005). A number of double patterning processes are proposed. One exemplary process involves a first set of exposure and development to form a photoresist pattern having lines and spaces at intervals of 1:3, processing the underlying layer of hard mask by dry etching, applying another layer of hard mask thereon, a second set of exposure and development of a photoresist film to form a line pattern in the spaces of the first exposure, and processing the hard mask by dry etching, thereby forming a line-and-space pattern at a half pitch of the first pattern. An alternative process involves a first set of exposure and development to form a photoresist pattern having spaces and lines at intervals of 1:3, processing the underlying layer of hard mask by dry etching, applying a photoresist layer thereon, a second set of exposure and development to form a second space pattern on the remaining hard mask portion, and processing the hard mask by dry etching. In either process, the hard mask is processed by two dry etchings.

While the former process requires two applications of hard mask, the latter process uses only one layer of hard mask, but requires to form a trench pattern which is difficult to resolve as compared with the line pattern. The latter process includes the use of a negative resist material in forming the trench pattern. This allows for use of high contrast light as in the formation of lines as a positive pattern. However, since the negative resist material has a lower dissolution contrast than the positive resist material, a comparison of the formation of lines from the positive resist material with the formation of a trench pattern of the same size from the negative resist material reveals that the resolution achieved with the negative resist material is lower. After a wide trench pattern is formed from the positive resist material by the latter process, there may be applied a thermal flow method of heating the substrate for shrinkage of the trench pattern, or a RELACS method of coating a water-soluble film on the trench pattern as developed and heating to induce crosslinking at the resist film surface for achieving shrinkage of the trench pattern. These have the drawbacks that the proximity bias is degraded and the process is further complicated, leading to reduced throughputs.

Both the former and latter processes require two etchings for substrate processing, leaving the issues of a reduced throughput and deformation and misregistration of the pattern by two etchings.

One method that proceeds with a single etching is by using a negative resist material in a first exposure and a positive resist material in a second exposure. Another method is by using a positive resist material in a first exposure and a negative resist material in a higher alcohol of 4 or more carbon atoms, in which the positive resist material is not dissolvable, in a second exposure. However, these methods using negative resist materials with low resolution entail degradation of resolution.

A method which does not involve PEB and development between first and second exposures is the simplest method with high throughput. This method involves first exposure, replacement by a mask having a shifted pattern drawn, second exposure, PEB, development and dry etching. However, the optical energy of second exposure offsets the optical energy of first exposure so that the contrast becomes zero, leading to a failure of pattern formation. If an acid generator capable of two photon absorption or a contrast enhancement layer (CEL) is used to provide nonlinear acid generation, then the energy offset is relatively reduced even when second exposure is performed at a half-pitch shifted position. Thus a pattern having a half pitch corresponding to the shift can be formed, though at a low contrast. See Jpn. J. Appl. Phy. Vol. 33 (1994) p 6874-6877, Part 1, No. 12B, December 1994.

The critical issue associated with double patterning is an overlay accuracy between first and second patterns. Since the magnitude of misregistration is reflected by a variation of line size, an attempt to form 32-nm lines at an accuracy of 10%, for example, simply requires an overlay accuracy within 3.2 nm. The advanced ArF immersion lithography scanner has an overlay accuracy of the order of 8 to 6 nm for every wafer on a common exposure tool. The term “every wafer” means that the exposure tool carries out alignment relative to a resist alignment pattern which has been formed by exposure and development. Herein a significant improvement in accuracy is necessary. If first and second exposures are carried out without demounting the wafer from the chuck, the positional shift associated with chuck remounting is cancelled and the alignment accuracy is improved to the order of 5 to 4 nm. In the case of double patterning, the process of carrying out plural exposures without demounting the wafer from the chuck becomes an exposure process which can be implemented on account of the improvement in alignment accuracy. In the exposure process intended to reduce the pitch to half by utilizing a nonlinear energy distribution such as the two-photon absorption resist, continuous exposure is carried out while shifting the exposure position by ¼ of the pitch and without demounting the wafer from the chuck. The nonlinear resist or CEL which is sensitive to radiation of 193 nm wavelength has not been reported. If such a resist were developed, the double exposure process with the minimum alignment error would become practical.

In addition to the double patterning technique, the technology for forming a fine space pattern or hole pattern includes use of negative resist material, thermal flow, and RELACS as mentioned above. The negative resist material suffers from the problems that the resist material itself has a low resolution and bridges form in a fine hole pattern because the negative resist material relies on the crosslinking system. The thermal flow and RELACS methods suffer from a likelihood of variation during dimensional shrinkage by heat.

FIG. 1 illustrates a process for forming a hole pattern using a positive photoresist material. In FIG. 4A, a photoresist material is coated onto a processable substrate 101 on a substrate 100 to form a photoresist film 102. In FIG. 4B, the photoresist film 102 is exposed to light through a photomask having the desired pattern and developed to form a photoresist pattern 102 a. In FIG. 4C, the processable substrate 101 is etched while using the photoresist pattern 102 a as a mask.

The method of forming a negative pattern by reversal of a positive pattern is well known from the past. For example, JP-A 2-154266 and JP-A 6-27654 disclose naphthoquinone resists capable of pattern reversal. JP-A 64-7525 describes exposure of selected portions of a film to focused ion beam (FIB) for curing and flood exposure whereby the cured portions are left behind. JP-A 1-191423 and JP-A 1-92741 describe exposure of a photosensitive agent of naphthoquinone diazide to form an indene carboxylic acid, heat treatment in the presence of a base into an indene which is alkali insoluble, and flood exposure to effect positive/negative reversal. FIG. 2 illustrates this positive/negative reversal method. In FIG. 2A, a photoresist material is coated onto a processable substrate 101 on a substrate 100 to form a photoresist film 102. In FIG. 2B, the photoresist film 102 is exposed to light through a photomask having the desired pattern and heated. In FIG. 2C, the photoresist film 102 is subjected to flood exposure. FIG. 2D illustrates pattern reversal by development to form a reversed pattern film 103. In FIG. 2E, the processable substrate 101 is etched while using the reversed pattern film 103 as a mask.

As to the positive/negative reversal method including exchange of developers, attempts were made to form negative patterns by development in an organic solvent of hydroxystyrene partially protected with tert-butoxycarbonyl (t-BOC) groups, and by development with super-critical carbon dioxide.

As to the positive/negative reversal method utilizing silicon-containing materials, it is proposed to form a fine hole pattern by covering a space portion of a positive resist pattern with a silicon-containing film, effecting oxygen gas etching for etching away the positive pattern portion, thus achieving positive/negative reversal to leave a silicon-containing film pattern. See JP-A 2001-92154 and JP-A 2005-43420. FIG. 3 illustrates this positive/negative reversal method. In FIG. 3A, a photoresist material is coated onto an underlayer film 104 on a processable substrate 101 on a substrate 100 to form a photoresist film 102. In FIG. 3B, the photoresist film 102 is exposed to light through a photomask having the desired pattern and developed to form a photoresist pattern 102 a. In FIG. 3C, the photoresist pattern 102 a is crosslinked. In FIG. 3D, a SOG film 105 is formed on the underlayer film 104 and so as to cover the crosslinked photoresist pattern 102 a. FIG. 3E illustrates light etching with CMP or CF gas until the crosslinked photoresist pattern 102 a is exposed. FIG. 3F illustrates pattern reversal by oxygen or hydrogen gas etching. In FIG. 3G, the processable substrate 101 is etched while using the patterned SOG film 105 as a mask.

As compared with the line pattern, the hole pattern is difficult to reduce the feature size. In order for the prior art method to form fine holes, an attempt is made to form fine holes by under-exposure of a positive resist film combined with a hole pattern mask, resulting in the exposure margin being extremely narrowed. It is then proposed to form holes of greater size, followed by thermal flow or RELACS method to shrink the holes as developed. However, there is a problem that control accuracy becomes lower as the pattern size after development and the size after shrinkage are greater and the quantity of shrinkage is greater. It is then proposed in Proc. SPIE, Vol. 5377, 255 (2004) that a pattern of X direction lines is formed using a positive resist film and dipole illumination, the resist pattern is cured, another resist material is coated thereon again, and a pattern of Y direction lines is formed in the other resist using dipole illumination, leaving a grid line pattern, spaces of which provide a hole pattern. Although a hole pattern can be formed at a wide margin by combining X and Y lines and using dipole illumination featuring a high contrast, it is difficult to etch vertically staged line patterns at a high dimensional accuracy. It is proposed in IEEE IEDM Tech. Digest 61 (1996) to form a hole pattern by exposure of a negative resist film through a Levenson phase shift mask of X direction lines combined with a Levenson phase shift mask of Y direction lines. Since the maximum resolution of ultrafine holes is determined by the bridge margin, the crosslinking negative resist film has the drawback that the threshold size is large as compared with the positive resist film.

As compared with white spots, a pattern of black spots can be formed to a fine size. As the hole size is reduced using a highly transparent halftone or chromeless phase shift mask, white spots are reversed into black spots, after which very small black spots with a high contrast are formed. It is reported in Proc. SPIE Vol. 4000, 266 (2000) to form dense fine holes by combining this concept with a negative resist film. A combination of a halftone phase shift mask having a high transmittance of 20% with a negative resist film provides a mask error enhancement factor (MEEF) of 0 (see Proc. SPIE Vol. 5040, 1258 (2003)).

When the super-resolution technology is applied to repeating dense patterns, the pattern density bias between dense and isolated patterns, known as proximity bias, becomes a problem. As the super-resolution technology used becomes stronger, the resolution of a dense pattern is more improved, but the proximity bias is exaggerated. In particular, an increase of proximity bias in a hole pattern poses a serious problem. One common approach taken to suppress the proximity bias is by biasing the size of a mask pattern. Since the proximity bias varies with properties of a photoresist material, specifically dissolution contrast and acid diffusion, the proximity bias of a mask varies with the type of photoresist material. For a particular type of photoresist material, a mask having a different proximity bias must be used. This adds to the burden of mask manufacturing. Then the pack and unpack (PAU) method is proposed in Proc. SPIE Vol. 5753, 171 (2005), which involves strong super-resolution illumination of a first positive resist to resolve a dense hole pattern, coating on the first positive resist pattern a negative resist film material in alcohol solvent which does not dissolve the first positive resist pattern, exposure and development of an unnecessary hole portion to close the corresponding holes, thereby forming both a dense pattern and an isolated pattern. One problem of the PAU method is misalignment between first and second exposures, as the authors point out in the report. The hole pattern which is not closed by the second development experiences two developments and thus undergoes a size change, which is another problem.

CITATION LIST

-   Patent Document 1: JP-A H02-154266 -   Patent Document 2: JP-A H06-027654 -   Patent Document 3: JP-A S64-7525 -   Patent Document 4: JP-A H01-191423 -   Patent Document 5: JP-A H01-092741 -   Patent Document 6: JP-A 2001-092154 -   Patent Document 7: JP-A 2005-043420 -   Patent Document 8: JP-A 2007-171895 -   Patent Document 9: JP-A 2006-293298 -   Non-Patent Document 1: Proc. SPIE Vol. 4690, xxix (2002) -   Non-Patent Document 2: Proc. SPIE Vol. 5040, 724 (2003) -   Non-Patent Document 3: Proc. SPIE Vol. 5754, 1508 (2005) -   Non-Patent Document 4: Jpn. J. App. Phys. Vol. 33 (1994), 6874-6877,     Part 1, No. 12B, December 1994 -   Non-Patent Document 5: Proc. SPIE Vol. 5377, 255 (2004) -   Non-Patent Document 6: IEEE IEDM Tech. Digest 61 (1996) -   Non-Patent Document 7: Proc. SPIE Vol. 4000, 266 (2000) -   Non-Patent Document 8: Proc. SPIE Vol. 5040, 1258 (2003) -   Non-Patent Document 9: Proc. SPIE Vol. 5753, 171 (2005)

DISCLOSURE OF THE INVENTION

When it is desired to form a very fine hole pattern, the double dipole lithography using a negative resist film and masks of X and Y direction line patterns suffers from the problems that the fine pattern cannot be formed due to low resolution as compared with a positive resist film, the throughput is reduced by two exposures involved, and a size difference arises between dense and isolated patterns. If a positive pattern once formed with a high resolution can be reversed into a negative pattern, the problems associated with the use of a negative resist film are overcome. If the exposure process capable of achieving through a single exposure a high resolution equivalent to the double dipole lithography is applicable, the problem of reduced throughput is overcome. The problem of a size difference between dense and isolated patterns is overcome by applying mask pattern correction or optical proximity correction (OPC) with a proximity bias taken into account.

As discussed above, a variety of methods were reported for reversal into a negative pattern of a positive image obtained from a positive resist film featuring a high resolution capability. In particular, the above-cited JP-A 2005-43420 refers to an organic solvent-based composition as the silicone-based burying material for positive/negative reversal. The previous method using a water-soluble silicon resin as the reversal film-forming material has the problem that if an organic solvent-based reversal film-forming material composition is coated onto a substrate having a positive pattern formed thereon, the positive pattern can be disrupted by the organic solvent used for coating. If the resist pattern-forming resin is insolubilized against organic solvent by curing the resist resin with EB or the like to induce crosslinking between molecules of the resist resin, then an organic solvent-based reversal film-forming material composition may be utilized, enabling a choice from a wider range of materials. Where this treatment is done, however, the removal of the resist pattern at the final stage for reversal cannot resort to removal by dissolution because the positive pattern has been insolubilized. The state-of-the-art technology relies on no other means than removal by reactive dry etching. Then a selectively dry etchable material containing silicon, titanium or the like must be selected as the reversal film-forming material. In one process, a silicon resin coated on a resist pattern is etched back with an etching gas such as fluorocarbon gas to expose the surface of the resist pattern, after which dry etching with oxygen and hydrogen gases is carried out for image reversal. For image reversal, two etching steps including etching back and etching and concomitant gas exchange are necessary. With this process, throughput is reduced.

On the other hand, JP-A 2001-92154 discloses advantageous removal of a positive pattern by wet etching. In the disclosed method, once a positive pattern is provided, an organic solvent solution of an organosilicon compound is directly (without any special treatment) coated to form a reversal film of organosilicon. The patent does not refer to the damage to the positive pattern by intermixing. The patent describes that for the preparation of an organosilicon composition, high polarity solvents (e.g., hydroxyl-bearing compounds such as propylene glycol monomethyl ether and lactic esters, esters such as PGMEA, and ketones such as acetone) may be utilized as well as low polarity solvents (e.g., toluene and cumene), although only toluene and cumene are used in Examples. The inventors made a follow-up test by using a solvent containing a high polarity solvent such as PGMEA, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether or cyclohexanone as the solvent for reversal film, and coating an organosilicon solution in such a solvent onto a positive pattern which had been subjected to no particular treatment. Then the pattern became dissolved in the coating solvent, and the test failed to achieve positive/negative reversal at the required accuracy level. It was demonstrated that this method can adopt only a reversal film-forming material exhibiting a high solubility in low polarity solvents, but not reversal film-forming materials having a high concentration of polar groups featuring substrate adhesion, such as novolac resins, polyhydroxystyrene polymers, and alicyclic polymers having a high content of hydroxy groups or lactone.

When a negative resist material is used in the double dipole lithography utilizing dense X direction lines and intersecting dense Y direction lines, a highly dense hole pattern approximately equivalent to the maximum resolution of lines is obtainable. The double dipole lithography, in the case of full-field exposure, requires two exposures while exchanging two masks. When it is desired to form a logic device pattern where dense pattern regions are combined with isolated pattern regions, two double dipole illumination exposures of dense pattern and one exposure of unnecessary pattern region are necessary, totaling to three exposures. A significant loss of throughput is unavoidable.

The state-of-the-art exposure system has one mask stage and is not constructed such that exposures are effected on a single wafer while exchanging three masks. Alignment is necessary whenever the mask is exchanged. The process time includes the times of three exposures plus the times of mask exchange and concomitant alignment, leading to a significant loss of throughput.

An object of the invention, which is made to achieve an improvement under the above-described circumstances, is to provide a process for forming a pattern including using a positive resist film, single exposure to form both a dense dot pattern and an isolated dot pattern, and positive/negative reversal of the dot pattern into a hole pattern.

By baking at high temperature the substrate having the positive dot pattern formed thereon such that the pattern is endowed with minimal necessary resistance to an organic solvent to be used in the reversal film-forming composition while it maintains a solubility in an alkaline etchant, there is provided a process for forming a hole pattern by way of positive/negative reversal wherein the step of finally forming a negative image is carried out by wet etching with an alkaline etchant. Then not only silicon base materials, but also organic non-silicone resins such as aromatic resins and polycyclic resins are applicable as the reversal film-forming composition. In addition, hydroxy-bearing solvents and highly polar solvents such as esters and ketones may be used as the solvent to formulate the reversal film-forming composition. There is provided a process for forming a pattern by way of positive/negative reversal that can form a hole pattern including both dense holes and isolated holes with a wide margin.

The inventor has found that by exposing a positive resist through a phase shift mask including lattice-arrayed shifters having different line size, a positive resist pattern consisting of dots only at the intersections between thick lines can be formed. That is, the inventor has discovered an exposure method capable of forming both dense and isolated dot patterns through a single exposure. If the resin in the positive resist pattern is subjected to partial crosslinking treatment, then crosslinking takes place to such an extent to provide necessary organic solvent resistance while maintaining a solubility in alkaline wet etchant. If the foregoing steps are incorporated in the negative pattern forming process relying on positive/negative reversal, then not only conventional silicon base materials, but also organic non-silicone resins such as aromatic resins and polycyclic resins are applicable as the reversal film-forming material. It then becomes possible to form a hole pattern including both dense and isolated holes through a single exposure.

[1] A process for forming a pattern by way of positive/negative reversal, comprising the steps of:

coating a chemically amplified positive resist composition onto a processable substrate, the resist composition comprising a resin comprising recurring units of structure having acid labile groups which are eliminatable with acid, the resin turning to be soluble in an alkaline developer as a result of elimination of the acid labile groups, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and optionally, a thermal acid generator capable of generating an acid upon heating, and an organic solvent, prebaking the coating to remove the unnecessary solvent and to form a resist film,

exposing the resist film to high-energy radiation through a phase shift mask including a lattice-like first shifter having a line width equal to or less than half a pitch and a second shifter arrayed on the first shifter and consisting of lines whose on-wafer size is 2 to 30 nm thicker than the line width of the first shifter, post-exposure baking so that the acid generated by the acid generator upon exposure may act on acid labile groups in the resin for thereby effecting elimination reaction of acid labile groups in the resin in exposed areas, developing the exposed resist film with an alkaline developer to form a positive pattern,

illuminating or heating the positive pattern, the acid generated by illumination or the heat serving to eliminate acid labile groups in the resin in the positive pattern for thereby increasing the alkaline solubility of the resin and to induce crosslinks in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent used in a reversal film-forming composition,

coating a reversal film-forming composition on the positive pattern-bearing substrate to form a reversal film, and

dissolving away the crosslinked positive pattern using an alkaline wet etchant.

[2] The process of [1] wherein the second shifter is arrayed on the first shifter. [3] The process of [1] or [2] wherein the second shifter is of crisscross or lattice-like shape. [4] The process of any one of [1] to [3] wherein the step of developing the exposed resist film is to form a pattern of dots only at the intersections between gratings of the second shifter. [5] The process of any one of [1] to [4] wherein the lattice-like first shifter is a halftone phase shift mask having a transmittance of 3 to 15%. [6] The process of any one of [1] to [5] wherein the phase shift mask includes the first shifter having a line width equal to or less than ⅓ of the pitch and the second shifter consisting of lines whose on-wafer size is 2 to 30 nm thicker than the line width of the first shifter. [7] The process of any one of [1] to [6] wherein in the step of illuminating or heating the positive pattern for increasing the alkaline solubility of the resin and for endowing the positive pattern with resistance to an organic solvent used in a reversal film-forming composition,

the dissolution rate of the crosslinked positive pattern in an alkaline wet etchant is such that the crosslinked positive pattern exhibits an etching rate in excess of 2 nm/sec when etched with 2.38 wt % TMAH aqueous solution,

the organic solvent used in the reversal film-forming composition is selected from the group consisting of propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and heptanone, and mixtures of two or more of the foregoing,

the resistance to organic solvent of the crosslinked positive pattern is such that the crosslinked positive pattern experiences a film slimming of up to 10 nm when contacted with the organic solvent for 30 seconds.

[8] The process of any one of [1] to [7] wherein said reversal film-forming composition comprises a resin comprising monomeric units of aromatic or alicyclic structure. [9] The process of any one of [1] to [8], further comprising, between the step of coating a reversal film-forming composition on the positive pattern-bearing substrate to form a reversal film and the step of dissolving away the crosslinked positive pattern using an alkaline wet etchant, the step of removing the reversal film deposited on the crosslinked positive pattern. [10] The process of [9] wherein the step of removing the reversal film deposited on the crosslinked positive pattern includes wet etching. [11] The process of [10] wherein the reversal film is soluble in an alkaline wet etchant, but has a dissolution rate which is slower than that of the crosslinked positive pattern after the step of endowing the positive pattern with resistance to organic solvent, the wet etching uses an alkaline wet etchant, and the step of removing the reversal film deposited on the crosslinked positive pattern and the step of dissolving away the crosslinked positive pattern are concurrently carried out. [12] The process of [11] wherein the reversal film has a dissolution rate of 0.02 nm/sec to 2 nm/sec when etched with 2.38 wt % TMAH aqueous solution. [13] The process of any one of [1] to [12] wherein said chemically amplified positive resist composition comprises a component capable of generating an acid in the step of heating for endowing the positive pattern with organic solvent resistance. [14] The process of [13] wherein the component capable of generating an acid is a thermal acid generator which is added to the resist composition in addition to the photoacid generator. [15] The process of [14] wherein the thermal acid generator has the general formula (P1a-2):

wherein R^(101d), R^(101e), R^(101f), and R^(101g) are each independently hydrogen, a straight, branched or cyclic C₁-C₁₂ alkyl, alkenyl, oxoalkyl or oxoalkenyl group, a C₆-C₂₀ aryl group, or a C₇-C₁₂ aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups, or R^(101d) and R^(101e), or R^(101d), R^(101e) and R^(101f) may bond together to form a ring with the nitrogen atom to which they are attached, each of R^(101e) and R^(101f) or each of R^(101d), and R^(101e) and R^(101f) is a C₃-C₁₀ alkylene group or a hetero-aromatic ring having incorporated therein the nitrogen atom when they form a ring, and K⁻ is a sulfonate having at least one α-position fluorinated, perfluoroalkylimidate or perfluoroalkylmethidate. [16] The process of any one of [1] to [15] wherein in said chemically amplified positive resist composition, the resin comprises recurring units having a lactone ring and recurring units having an acid labile group which is eliminatable with acid. [17] The process of any one of [1] to [16] wherein in said chemically amplified positive resist composition, the resin comprises an electrophilic partial structure such as an ester group or cyclic ether which will form crosslinks in the resin of the positive resist pattern. [18] The process of [17] wherein in said chemically amplified positive resist composition, the resin comprises recurring units having a 7-oxanorbornane ring and recurring units having an acid labile group which is eliminatable with acid, and heat is applied in the step of illuminating the positive pattern to generate an acid whereby elimination of acid labile groups and crosslinking of the resin take place simultaneously in the positive pattern. [19] The process of [18] wherein the recurring units having a 7-oxanorbornane ring are recurring units (a) having the general formula (1):

wherein R¹ is hydrogen or methyl, R² is a single bond or a straight, branched or cyclic C₁-C₆ alkylene group which may have an ether or ester radical, and which has a primary or secondary carbon atom through which it is linked to the ester group in the formula, R³, R⁴, and R⁵ are each independently hydrogen or a straight, branched or cyclic C₁-C₆ alkyl group, and “a” is a number in the range: 0<a<1.0. [20] The process of any one of [16] to [19] wherein the recurring units having an acid labile group which is eliminatable with acid are recurring units (b) having the general formula (2):

wherein R⁶ is hydrogen or methyl, R⁷ is an acid labile group, and b is a number in the range: 0<b≦0.8. [21] The process of [20] wherein the acid labile group of R⁷ is an acid labile group of alicyclic structure which is eliminatable with acid. [22] The process of any one of [1] to [21] wherein the positive pattern comprises a dot pattern, and the pattern resulting from positive/negative reversal comprises a hole pattern. [23] The process of any one of [1] to [22] wherein the positive pattern comprises both a dense dot pattern and an isolated dot pattern, and the pattern resulting from positive/negative reversal comprises both a dense hole pattern and an isolated hole pattern. [24] The process of [23] wherein a dense dot pattern and an isolated dot pattern are formed as the positive pattern by exposure to a dense dot pattern and subsequent exposure to an unnecessary portion of the dot pattern, and a dense hole pattern and an isolated hole pattern are formed by positive/negative reversal therefrom. [25] A process for forming a pattern by way of positive/negative reversal according to [1], comprising the steps of:

coating a chemically amplified positive resist composition onto a processable substrate, said resist composition comprising a resin comprising recurring units having acid labile groups which are eliminatable with acid, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and a solvent, heating to remove the unnecessary solvent to form a resist film,

coating a protective film-forming composition onto the resist film and drying to form a protective film,

exposing the resist film to high-energy radiation in a repeating dense pattern from a projection lens, by immersion lithography with water or a transparent liquid having a refractive index of at least 1 intervening between the resist film and the projection lens, further exposing an unnecessary region of the dense pattern or unexposed area by immersion lithography, post-exposure baking for causing the acid generated by the acid generator upon exposure to act on the acid labile groups on the resin whereby the acid labile groups on the resin in the exposed area undergo elimination reaction, and developing the exposed resist film with an alkaline developer to form a positive pattern,

treating the positive pattern so as to eliminate the acid labile groups on the resin in the positive pattern resulting from the previous step, and to induce crosslinking in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition,

coating a reversal film-forming composition thereon to form a reversal film, and

dissolving away the positive pattern using an alkaline wet etchant.

[26] The process of [25] wherein said protective film-forming composition is based on a copolymer comprising amino-containing recurring units. [27] The process of [25] or [26] wherein said protective film-forming composition further comprises an amine compound. [28] The process of any one of [1] to [27], further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, forming a silicon-containing intermediate film thereon, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a hydrocarbon-based material. [29] The process of any one of [1] to [27], further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a silicon-containing material. [30] The process of [29], further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, forming an organic antireflection film thereon, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a silicon-containing material.

FIG. 5 illustrates an aperture configuration in a dipole illumination exposure tool applied in combination with a mask of Y-direction line pattern as shown in FIG. 6. FIG. 7 illustrates an aperture configuration in a dipole illumination exposure tool applied in combination with a mask of X-direction line pattern as shown in FIG. 8. The shape of opening may be circular as shown in FIG. 5, elliptic as shown in FIG. 9, or arc as shown in FIG. 10.

FIG. 11 illustrates an optical image of Y-direction lines having a pitch of 80 nm and a line size of 40 nm printed using ArF excimer laser of 193 nm wavelength, NA 1.3 lens, dipole illumination, 6% halftone phase shift mask, and s-polarization. FIG. 12 illustrates an optical image of X-direction lines having a pitch of 80 nm and a line size of 40 nm printed using ArF excimer laser of 193 nm wavelength, NA 1.3 lens, dipole illumination, 6% halftone phase shift mask, and s-polarization. A black area corresponds to a light-shielded region and a white area corresponds to an intense light region. FIG. 13 is a contrast image obtained by overlaying the optical image of X-direction lines on that of Y-direction lines. Against the expectation that a combination of X and Y lines may form a lattice-like image, weak light areas draw circular figures. As the size of a circle increases, the figure approaches to rhombus, tending to merge with adjacent figures. As the size of a circle becomes smaller, circularity is improved.

FIG. 14 illustrates a simulation of a pattern profile of a resist film on the basis of the optical image of FIG. 13. Herein, Z direction is the negative of logarithm of a dissolution rate of the resist film, reflecting the pattern profile of the resist film. It is shown that a 80-nm pitch dot pattern of the positive resist film can be formed using the double dipole lithography including two exposures of X and Y lines.

FIG. 15 illustrates the layout of a mask having a lattice-like pattern consisting of X and Y lines. A black area is a halftone shifter.

FIG. 16 illustrates an aperture configuration employed in cross-pole illumination corresponding to the lattice-like mask pattern of X and Y lines.

FIG. 17 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 20 nm as on-wafer size, under conditions: ArF excimer laser of 193 nm wavelength, NA 1.3 lens, cross-pole illumination, 6% halftone phase shift mask (of the layout shown in FIG. 15), and azimuthally polarized illumination. FIG. 18 is a resist profile simulation. The resist used herein has a sensitivity of 30 mJ/cm².

FIG. 19 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 25 nm. FIG. 20 is a resist profile simulation. The resist used herein has a sensitivity of 50 mJ/cm².

FIG. 21 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 30 nm. FIG. 22 is a resist profile simulation. The resist used herein has a sensitivity of 80 mJ/cm².

As the width of lines in the lattice-like pattern increases, the intensity of light in the light-shielding portion is reduced, the sensitivity of resist becomes lower, and the film retention of dot pattern is increased.

FIG. 23 is a resist profile simulation of a lattice-like pattern having a pitch of 90 nm and a line width of 20 nm in an exposure dose of 50 mJ/cm². FIG. 24 is a resist profile simulation of the same lattice-like pattern in an exposure dose of 80 mJ/cm². It is seen that on use of masks of lattice-like pattern having a line width of 20 nm and 25 nm, if the optimum exposure dose is matched with that for the line width of 25 nm, the pattern corresponding to the line width of 20 nm is not formed because it is entirely dissolved. This is also true when masks of lattice-like pattern having a line width of 20 nm and 30 nm are used.

A thin lattice-like pattern is formed on the entire surface of a mask, and a thick lattice-like or cross pattern is located where a dot pattern is to be formed. No dots are formed at thin gratings, but dots are formed only at thick gratings. The thin lattice-like pattern functions as an auxiliary pattern for increasing the contrast of the thick lattice-like pattern. This permits both a dense pattern and an isolated pattern to be formed through a single exposure in a common exposure dose.

As shown in FIG. 25, on a lattice-like pattern having a pitch of 90 nm and a line width of 20 nm, thick crisscross or intersecting line segments are disposed where dots are to be formed. A black area corresponds to the halftone shifter portion. Line segments with a width of 30 nm are disposed in the dense pattern portion whereas thicker line segments (width 40 nm in FIG. 25) are disposed in more isolated pattern portions. Since the isolated pattern provides light with a lower intensity than the dense pattern, thicker line segments are used. Since the peripheral area of the dense pattern provides light with a relatively low intensity, line segments having a width of 32 nm are assigned to the peripheral area which width is slightly greater than that in the internal area of the dense pattern.

FIG. 26 shows an optical image from the mask of FIG. 25. Black or inked areas are where dots of the resist pattern are formed. Black spots are found at positions other than where dots are formed, but few are transferred in practice because they are of small size. Optimization such as reduction of the width of grating lines corresponding to unnecessary dots can inhibit transfer of unnecessary dots. FIG. 27 illustrates a resist profile simulation based on the optical image of FIG. 26. It is demonstrated that both dense dots and isolated dots can be formed at an exposure dose of 70 mJ/cm².

When dots are formed by the prior art method, a mask having a dot pattern is used. FIG. 28 shows the layout of a mask having a dot pattern. Black areas are halftone shifters. The pattern size for isolated dots is greater than that for dense dots, which reduces proximity bias. Squares for dense dots have one side with a size of 55 nm whereas squares for isolated dots have one side with a size of 90 nm, indicating a bias of 35 nm. In contrast, the mask pattern of FIG. 25 includes dense dot-forming lines having a size of 30 nm and isolated dot-forming lines having a width of 40 nm, with a bias of 10 nm. Since the optimum bias varies with the properties of resist as well, it is advantageous that the mask bias is as small as possible.

FIG. 29 shows an optical image from the mask of FIG. 28. No black spots are present in the light-shielded portion of FIG. 29, indicating lower light-shielding property than the image of FIG. 26. FIG. 30 illustrates a resist profile computed on the basis of the optical image of FIG. 29. The film retention of dot pattern is reduced as compared with FIG. 27, which is accounted for by the absence of a strongly light-shielded portion in FIG. 29. A reduction in film retention of dot pattern raises the problem that when a reversal film is coated thereon and treated for reversal, reversal dissolution does not proceed.

The pack and unpack (PAU) method involves coating a positive resist film, first exposure to form a dense hole pattern, coating thereon a negative resist film material in water or alcohol solvent which does not dissolve the positive resist pattern, and second exposure for erasing an unnecessary hole pattern portion. Since a dense hole pattern with uniform size is initially formed, the PAU method is also devoid of proximity bias. Since the first exposure is exposure of a hole pattern, the PAU method is not improved in resolution over the conventional exposure method and only proximity bias is eliminated. In contrast, the pattern forming process of the invention permits both dense and isolated dot patterns to be formed through a single exposure using a mask having a high contrast lattice-like line pattern, and is thus significantly improved in resolution over the conventional hole forming method and also in throughput over the PAU method involving two exposures.

ADVANTAGEOUS EFFECTS OF INVENTION

As compared with the method of forming fine holes by combining the double dipole lithography with a negative resist film, the pattern forming process of the invention is capable of forming a hole pattern by using a positive resist film, effecting a single exposure to form a dot pattern at the same level of resolution as the double dipole lithography, and effecting positive/negative reversal to form the hole pattern. Use of a positive resist film which has a higher resolution capability than a negative resist film offers improvements in resolution and process margins such as focus margin and exposure margin. Since positive/negative reversal is carried out by wet etching with a developer, the process achieves a high throughput as compared with the conventional dry development and eliminates a need for an etching system for dry development. Although the double dipole lithography needs two masks, the inventive process uses a single phase shift mask having a lattice-like pattern of lines with different width. Additionally, the process achieves a level of resolution equivalent to the double dipole lithography and permits both dense and isolated patterns to be formed through a single exposure.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 schematically illustrates in cross-sectional views a prior art process for forming a hole pattern through exposure of a positive photoresist material, FIG. 1A shows formation of a photoresist film, FIG. 1B shows exposure and development of the photoresist film, and FIG. 1C shows etching of a processable substrate.

FIG. 2 schematically illustrates in cross-sectional views a prior art image reversal process using a positive i or g-line resist material based on a quinonediazide-novolac resin, FIG. 2A shows formation of a photoresist film, FIG. 2B shows exposure and heating of the photoresist film, FIG. 2C shows flood exposure, FIG. 2D shows pattern reversal by development, and FIG. 2E shows etching of a processable substrate.

FIG. 3 schematically illustrates in cross-sectional views a prior art image reversal process involving hardening of a developed resist film and burying of SOG film, FIG. 3A shows formation of a photoresist film, FIG. 3B shows exposure and development of the photoresist film, FIG. 3C shows crosslinking of the photoresist film, FIG. 3D shows coating of a SOG film, FIG. 3E shows light etching with CMP or CF gas, FIG. 3F shows pattern reversal by oxygen/hydrogen gas etching, and FIG. 3G shows etching of a processable substrate.

FIG. 4 schematically illustrates in cross-sectional views the pattern forming process of the invention, FIG. 4A shows that a processable substrate and a resist film are disposed on a substrate, FIG. 4B shows that the resist film is exposed and developed, FIG. 4C shows that the resist pattern is deprotected and crosslinked under the action of acid and heat, FIG. 4D shows that a pattern reversal film is coated, FIG. 4E shows that the pattern reversal film is developed for positive/negative reversal, and FIG. 4F shows that the processable substrate is etched using the positive/negative reversal pattern.

FIG. 5 illustrates an aperture configuration in an exposure tool used in Y dipole illumination exposure.

FIG. 6 illustrates a Y-direction line pattern of the mask used in Y dipole illumination.

FIG. 7 illustrates an aperture configuration in an exposure tool used in X dipole illumination exposure.

FIG. 8 illustrates a X-direction line pattern of the mask used in Y dipole illumination.

FIG. 9 illustrates apertures of elliptic shape in an exposure tool used in Y dipole illumination exposure.

FIG. 10 illustrates apertures of arc shape in an exposure tool used in Y dipole illumination exposure.

FIG. 11 illustrates a light intensity distribution under conditions: NA 1.3 lens, dipole illumination, s-polarized illumination, and 6% halftone phase shift mask of Y-direction lines, wherein a darker inked area indicates a weaker light intensity.

FIG. 12 illustrates a light intensity distribution under conditions: NA 1.3 lens, dipole illumination, s-polarized illumination, and 6% halftone phase shift mask of X-direction lines, wherein a darker inked area indicates a weaker light intensity.

FIG. 13 illustrates a light intensity distribution of double dipole exposure obtained by overlaying the X-direction lines of FIG. 12 on the Y-direction lines of FIG. 11 both with NA 1.3 lens, wherein a darker inked area indicates a weaker light intensity.

FIG. 14 illustrates a simulation of a resist profile of double dipole illumination lithography with NA 1.3 lens wherein Z axis is the negative of logarithm of a dissolution rate of the resist, reflecting the resist profile of dot pattern, and the exposure dose is 20 mJ/cm².

FIG. 15 illustrates a lattice-like mask pattern of X and Y lines wherein a black area is a halftone shifter.

FIG. 16 illustrates an aperture configuration in a cross-pole illumination exposure tool applied to the mask of X-Y line lattice-like pattern.

FIG. 17 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 20 nm under conditions: NA 1.3 lens, cross-pole illumination, 6% halftone phase shift mask, and azimuthally polarized illumination.

FIG. 18 is a resist profile simulation corresponding to the optical image of FIG. 17 wherein the exposure dose is 30 mJ/cm².

FIG. 19 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 25 nm under conditions: NA 1.3 lens, cross-pole illumination, 6% halftone phase shift mask, and azimuthally polarized illumination.

FIG. 20 is a resist profile simulation corresponding to the optical image of FIG. 19 wherein the exposure dose is 50 mJ/cm².

FIG. 21 is a simulation of an optical image of a lattice-like pattern having a pitch of 90 nm and a line width of 30 nm under conditions: NA 1.3 lens, cross-pole illumination, 6% halftone phase shift mask, and azimuthally polarized illumination.

FIG. 22 illustrates a resist profile simulation corresponding to the optical image of FIG. 21 wherein the exposure dose is 80 mJ/cm².

FIG. 23 illustrates a resist profile simulation corresponding to the optical image of FIG. 17 wherein the exposure dose is 50 mJ/cm².

FIG. 24 illustrates a resist profile simulation corresponding to the optical image of FIG. 17 wherein the exposure dose is 80 mJ/cm².

FIG. 25 illustrates a lattice-like mask pattern of X and Y lines having a dot pattern disposed thereon, wherein black areas are 6% halftone shifters.

FIG. 26 is an optical image produced under conditions: NA 1.3 lens, cross-pole illumination, azimuthally polarized illumination, and halftone phase shift mask of FIG. 25.

FIG. 27 illustrates a resist profile simulation corresponding to the optical image of FIG. 26.

FIG. 28 illustrates a dot mask pattern including dots of different size wherein black areas are 6% halftone shifters.

FIG. 29 is an optical image produced under conditions: NA 1.3 lens, cross-pole illumination, azimuthally polarized illumination, and 6% halftone phase shift mask of FIG. 28.

FIG. 30 illustrates a resist profile simulation corresponding to the optical image of FIG. 29.

FIG. 31 illustrates a mask pattern in which arrowed lattice-like shifters (and dots) are staggered.

FIG. 32 illustrates a resist profile simulation produced under conditions: NA 1.3 lens, cross-pole illumination, azimuthally polarized illumination, and mask of the layout of FIG. 25 having the same line width and a reduced pitch of 80 nm.

FIG. 33 illustrates a resist profile simulation produced under conditions: NA 1.3 lens, cross-pole illumination, azimuthally polarized illumination, and mask of the layout of FIG. 28 having the same line width and a reduced pitch of 80 nm.

FIG. 34 illustrates a mask pattern used in Examples 1 and 2 and also indicates size measuring positions in a corresponding resist pattern.

FIG. 35 illustrates a mask pattern used in Comparative Example 1 and also indicates size measuring positions in a corresponding resist pattern.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.

“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

As used herein, the notation (C_(n)-C_(m)) means a group containing from n to m carbon atoms per group.

The abbreviations and acronyms have the following meaning.

Mw: weight average molecular weight

Mn: number average molecular weight

Mw/Mn: molecular weight distribution or dispersity

GPC: gel permeation chromatography

PEB: post-exposure baking

CVD: chemical vapor deposition

SOG: spin on glass

TMAH: tetramethylammonium hydroxide

PGMEA: propylene glycol monomethyl ether acetate

The abbreviation “phr” refers to parts by weight per 100 parts by weight of resin or polymer.

The process of the invention includes the step of exposing the resist film to high-energy radiation through a phase shift mask having a lattice-like halftone shifter pattern. Specifically, the phase shift mask has a lattice-like halftone shifter pattern in which cross or lattice-like patterns thicker than the width of vertical and horizontal gratings are formed preferably at intersections between vertical and horizontal gratings. A lattice-like pattern is formed where no dots are to be formed as well, while first shifter gratings where no dots are to be formed have a thin line width and second shifter gratings where dots are to be formed have a thick line width. The line width difference between the first shifter and the second shifter is 2 to 30 nm, preferably 2 to 20 nm, and more preferably 3 to 15 nm. Preferably the width of the first shifter is 5 to 40 nm thinner than the half-pitch. For an array of gratings at a pitch of 90 nm, the first shifter has a width of about 10 to 20 nm, and the second shifter has a width of about 25 to 50 nm. The width of the second shifter is preferably about 25 to 35 nm, more preferably about 30 nm in the case of dense patterns, and preferably about 35 to 45 nm, more preferably about 40 nm in the case of isolated patterns. The halftone shifters have a transmittance of 3 to 15%, preferably 4 to 10%. If the pitches of the first shifter are all the same, the best contrast improving effect is exerted. Since the second shifter must be arrayed on the first shifter, the position of dots in positive resist is limited to a multiple of the half-pitch of the shifter. If dots are formed at positions staggered from the multiple position of the half-pitch, a mask having some second shifters staggered from the first shifter as indicated by the arrows in FIG. 31 may be used.

On use of a mask of X-Y gratings, the illumination of the exposure tool is most preferably a combination of cross-pole illumination through the apertures shown in FIG. 16 with X-Y polarized illumination. Instead of X-Y polarized illumination, azimuthally polarized illumination may be employed. Although the azimuthally polarized illumination is ring-like annular polarized illumination, its combination with cross-pole illumination with only the outermost periphery of crisscross in X and Y directions being cut out exerts substantially the same effect as the X-Y polarized illumination.

Instead of cross-pole illumination, two exposures by X-Y dipole illumination through the apertures shown in FIGS. 7 and 5, respectively, may be performed. Although the resultant effect is substantially the same as the cross-pole illumination, the two dipole exposures is disadvantageous in throughput.

On use of an oblique 45 degree lattice mask, the illumination is a combination of oblique 45 degree cross-pole illumination with azimuthally polarized illumination. Instead of cross-pole illumination, annular illumination may be used in combination with azimuthally polarized illumination, and hexa-pole or octa-pole illumination may be combined with azimuthally polarized illumination. Alternatively, annular illumination having a small circle or annulus at the center, cross-pole, hexa-pole, or octa-pole illumination may be used. Although polarized illumination may not be used, a pattern with a finer pitch can be formed using polarized illumination. A pattern with the finest pitch can be formed from a combination of a X-Y lattice mask, cross-pole illumination (inter alia, the outermost periphery cut out at an angle of up to 35 deg, preferably up to 25 deg) and X-Y polarized illumination.

The resolution limit of a line pattern is in principle equal to the wavelength divided by lens' NA and 4. In an example of ArF lithography with 193 nm wavelength and a NA 1.30 lens, the maximum resolution is 37.1 nm. Actually, polarized illumination has a modification which is not equal to 100%, and the cutout angle of dipole illumination is difficulty reduced below 20%. It is then impossible to form an ideal optical image. A very fine pattern is largely affected by the resolution capability of a resist film. For these reasons, actually the maximum resolution is 38 nm in pinpoint, and the maximum resolution with a certain margin is 39 nm.

Nevertheless, a simulation as shown in FIG. 32 attests that using the pattern forming process of the invention, dots at the same half-pitch of 40 nm as lines can be resolved despite two-dimensional pattern. Both dense and isolated patterns can be formed at the same time through a single exposure. In FIG. 32, a computation is performed using a mask having the same line width as in the mask of FIG. 25, but a pitch reduced from 90 nm to 80 nm. The results of computation of a resist profile using a mask having the same dot size as in the mask of FIG. 28, but a pitch of 80 nm are shown in FIG. 33. Outstanding film slimming of isolated patterns and mergence of dense patterns are seen, indicating that the desired pattern may not be formed.

As discussed above, several attempts have already been made to form a pattern, which is optically disadvantageous to form from a positive resist material as such, using a positive resist material featuring a high resolution capability and positive/negative reversal. There were many problems to be overcome in the course of development works. In the situation where a reversal film is formed on a once formed positive pattern, how to deposit a new coating without disrupting the underlying pattern is one of such problems. The initial approach addressing this problem is to use an aqueous composition in which the positive pattern is not dissolvable, as the reversal film-forming composition. The reversal film material which can be used is limited to a narrow range of water-soluble materials. Then JP-A 2005-43420 proposes EB curing, by which a positive pattern is crosslinked to be insoluble in solvents and developers before a reversal film is formed. Another problem is how to selectively remove the positive pattern relative to the reversal film. Selective removal is achieved using SOG and organic silicone materials having resistance to oxygen dry etching as the reversal film as taught in JP-A 2005-43420.

On the other hand, the fact that a resist film as shown in JP-A 2005-43420 is crosslinked and insolubilized upon exposure to high-energy radiation was known at the initial phase of research and development of chemically amplified resist materials as a phenomenon that occurs when a chemically amplified resist film is exposed to radiation of too high energy. That is, it is a phenomenon that when polyhydroxystyrene units of which a chemically amplified resist polymer is composed are exposed to high intensity light, a hydrogen radical is eliminated from the methine to which the phenyl group is bonded, and the resulting radical acts to form crosslinks between resin molecules whereby the resin is insolubilized. It is believed that this radical creation capable of inducing crosslink formation can occur not only on the styrene structure, but also on the polyacrylic acid structure. It is further believed that similar crosslink formation occurs on methylene bonded to a heteroatom. However, the inventors observed that when light exposure is made stepwise, insolubilization of a resist film by crosslink formation does not instantly occur, but past consecutive points of time when the dissolution rate is slightly reduced, and attempted to utilize this phenomenon. More particularly, the initially observed reductions of dissolution rate are results of crosslinks forming within or between molecules within a limited range. As long as crosslinking is within the limited range, there is a possibility that resistance to organic solvents such as the coating solvent is obtainable without completely losing a dissolution rate in alkaline developer. Then, studying to form a pattern having resistance to organic solvents commonly used in film-forming compositions without completely losing a dissolution rate in alkaline developer, the inventors have found that such a pattern is feasible.

If the method of endowing a positive pattern with resistance to organic solvents without completely losing solubility in alkaline developer as mentioned above is incorporated in the process of forming a resist pattern through positive/negative reversal, a pattern forming process involving reversal of a positive pattern to a negative pattern becomes possible as described below. Namely, in accordance with the ordinary positive pattern forming method, first a chemically amplified positive resist composition is coated and prebaked to form a resist film. Then patternwise exposure is performed, and post-exposure heating or baking is performed to eliminate acid labile groups from the resin in the exposed area, for thereby turning the exposed area soluble in alkaline developer. This is followed by development with an alkaline developer, yielding a positive pattern. Next, the resulting positive pattern is subjected to the step of endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition without completely losing solubility in the alkaline developer. Next, on the substrate having the positive pattern endowed with resistance to an organic solvent to be used in a reversal film-forming composition, the reversal film-forming composition in the form of a solution in that organic solvent is coated to form a reversal film. At this point, the reversal film is coated so as to completely bury or fill spaces in the positive pattern, although the reversal film may be coated so as to form a layer over the positive pattern as well. In such an event, as described in JP-A 2001-92154 and JP-A 2005-43420, after the reversal film is formed, the portion of the reversal film deposited on the positive resist is removed and the positive pattern is then removed using an alkaline wet etchant. Then only the portion of the reversal film where the positive pattern is absent is left behind, that is, a reversal film pattern reflecting positive/negative reversal is obtained. It is noted that the alkaline wet etchant serves to dissolve the positive pattern, and the developer for forming the positive pattern may be used as the etchant while its concentration may be adjusted if necessary.

The resist pattern forming process relying on positive/negative reversal according to the invention achieves significant simplification of operation because the removal of the positive pattern does not need conventional oxygen dry etching. Further, the reversal film which can be used in the process may be any of conventional organic films including antireflective coatings (ARC) of aromatic organic polymers and organic underlayer films used in the multilayer resist process, specifically organic films comprising resins containing a majority of aromatic structure-bearing units well-known in the art, for example, novolac resins (see JP-A 2007-171895), polystyrene resins, vinyl ether or acrylic resins containing anthracene or naphthalene rings, and multi-branched resins (also known as aliphatic polycyclic structure resins) as used in the ArF resist (see JP-A 2006-293298). Of course, these reversal films may be either films which are insolubilized in organic solvents through crosslink formation during deposition like the ARC or films which are not insolubilized in such a manner, as long as a difference in dissolution rate enough to provide an etching selectivity with respect to the alkaline wet etchant is available between the reversal film and the positive pattern. If these organic material films are used, reversal film patterns resulting from reversal can be directly used as the etching mask for processing metallic silicon and silicon oxide substrates, like the conventional organic resist patterns. Furthermore, as is well known in the art, when organic reversal films as described above are used, films and substrates of silicon nitride, silicon oxynitride, titanium oxide, titanium nitride, germanium oxide and hafnium oxide may be processed as well as the metallic silicon and silicon oxide substrates.

Furthermore, if the reversal film used is a film having a scarce alkaline solubility as will be described later, the step of removing the reversal film deposited on the positive resist pattern may resort to the step of dissolving away in an alkaline wet etchant rather than conventional dry etching and organic solvent stripping techniques. When removal is made by this technique, the reversal film deposited on the resist pattern and the resist pattern can be concurrently removed by a single operation, achieving a significant step saving to the overall process.

The positive pattern is endowed with resistance to an organic solvent to be used in the reversal film-forming composition without completely losing solubility in alkaline wet etchant, and then the positive pattern is prevented from being dissolved and hence deformed or disrupted during coating and formation of the reversal film. This can be achieved by illumination of high-energy radiation of an appropriate energy level, as discussed above. Recognizing that the crosslink formation by light or illumination is sometimes difficult to control owing to the tolerance of illumination dose and the uniformity of illumination, the inventors sought for another crosslink forming technique and discovered that a limited degree of crosslinking just to impart the desired organic solvent resistance can be achieved by heat. Particularly when a positive pattern obtained from a resist material having units having a crosslinking capability under strong reaction conditions such as lactone structure is used, the desired control is relatively easily achievable by heat in the presence of acid.

The step of heating the positive pattern for endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition without losing a solubility in an alkaline wet etchant differs in the amount of acid to be generated and the optimum temperature to be reached by heating, depending on a particular resist material used. Nevertheless, the resist pattern forming process of the invention may be readily implemented by setting conditions for this step in accordance with the following measures. Namely, acid is generated within the resist film by illuminating light or high-energy radiation such as electron beam (EB) in an appropriate range to the resist film and then heating, or solely by heating, whereupon the acid is used to eliminate acid labile groups in the resin to impart a solubility in alkaline solution to the resin. At the same time as this treatment, partial crosslinks are formed by light or heat, whereby the resin is endowed with resistance to an organic solvent to be used in a reversal film-forming composition. Preferably, the measure of solubility of the resist film to be achieved by this step is that the resist film has an etching rate in excess of 2 nm/sec when etched with a 2.38 wt % TMAH aqueous solution commonly used in the alkaline development of resist films. Also, the resistance to an organic solvent to be used in a reversal film-forming composition is of such order that the resist pattern after the resistance-endowing (or crosslinking) treatment experiences a thickness reduction of up to 10 nm when contacted with a solvent to be used in a reversal film-forming composition for 30 seconds and more preferably for 60 seconds, and the solvent resistance of such order prevents the occurrence of the problem that the pattern of the positive resist film is fatally damaged when the reversal film-forming composition is coated thereon, and hence, a reversed (negative) pattern of the desired configuration is not obtainable. It is noted that in determining the treatment conditions, if a bulk film is used which has passed the above-described sequence of steps including resist coating, prebaking, and PEB, but excluding only pattern exposure for positive pattern formation, and has further been subjected to a set of conditions constituting a candidate step of endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition without losing a solubility in an alkaline wet etchant, then the two dissolution rates described above are readily determined.

The organic solvent used in the reversal film-forming composition which allows for advantageous use of the invention may encompass those solvents in which reversal film-forming organic polymers are fully soluble, and which offer good coating properties, for example, the above-described hydroxy-bearing solvents, esters, ketones and the like. Specifically, the solvent is selected from among PGMEA, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and heptanone, which may be used alone or in admixture of two or more. If desired, alcohols of 3 to 10 carbon atoms, toluene, xylene, anisole or the like may be added to one or more of the foregoing solvents. Then as to the measure of endowing resistance to the organic solvent used in the reversal film-forming composition, the resist pattern which has been treated to have such a degree of solvent resistance as to experience a thickness reduction (or film slimming) of up to 10 nm when contacted with a single solvent or a mixture of solvents selected from the above-mentioned group for 30 seconds and more preferably for 60 seconds is particularly preferred because of versatile use.

When partial crosslinks are induced by illumination of high-energy radiation, the heating treatment of the positive pattern may be heating to the PEB temperature used in forming the positive pattern or somewhat lower temperature, because the only reaction to be induced by heating is decomposition of acid labile groups. However, when high-energy radiation is not used, or when the main purpose of high-energy radiation is to generate acid, that is, when an energy amount equivalent to that of pattern exposure in the previous step is used and crosslinks are formed mainly by thermally induced reaction, it is preferable to select a higher temperature than the prebaking temperature used in formation of the resist film or the PEB temperature. In the case of a material for which this temperature is set lower than the heating of the previous step, there is a risk of the positive resist film decreasing its resolution.

The positive/negative reversal process is advantageously utilized in the following case. As for the positive pattern, a finer size pattern can be formed with an over-exposure dose. Then, although it is technically quite difficult to form isolated spaces (trench pattern) below the exposure limit, for example, a very fine trench pattern can be formed by utilizing over-dose exposure to form a finer size pattern below the ordinary exposure limit and reversing the resulting pattern in accordance with the inventive process. Moreover, although formation of a fine hole pattern encounters more technical difficulty than the trench pattern, holes of a very small size can be formed by utilizing over-dose exposure to form a fine dot pattern and reversing the resulting pattern in accordance with the inventive process.

Now referring to one typical embodiment of the invention wherein a material having a scarce solubility in an alkaline wet etchant is used as the reversal film, the invention is described in further detail. As used herein, the term “alkaline wet etchant” is substantially equivalent to an alkaline developer used in the development of resist patterns and thus often referred to as “alkaline developer” as well.

In the most preferred embodiment of the invention, the pattern forming process comprises the steps of coating a positive resist composition onto a substrate, said resist composition comprising a polymer (or base resin) comprising recurring units, preferably of alicyclic structure, having acid labile groups which are eliminatable with acid, the polymer turning, as a result of elimination of acid labile groups and crosslinking, into a crosslinked polymer having a dissolution rate in excess of 2 nm/sec in an alkaline developer, prebaking the resist composition to form a resist film, exposing a selected portion of the resist film to high-energy radiation, PEB, and developing the exposed resist film with the alkaline developer to form a positive pattern. Thereafter, the positive pattern is treated so as to generate acid and heated, thereby eliminating acid labile groups from the polymer and inducing crosslinking in the polymer in the positive pattern. Then, a reversal film having a dissolution rate of 0.02 nm/sec to 2 nm/sec in the alkaline developer is formed on the substrate to cover the resist pattern. The alkaline developer is then applied thereon to dissolve a surface layer of the reversal film and dissolve away the resist pattern, providing the reversal film with a pattern which is a reversal of the resist pattern.

In this embodiment, a hole pattern can be formed by forming a dot pattern as the resist pattern, followed by reversal.

Preferably crosslink formation is attributed to electrophilic structures such as ester groups and cyclic ethers in the resin. Under the action of acid and heat, crosslinking reaction takes place by reactions such as ester exchange, ring-opening, esterification and etherification of lactone ring, or ring-opening, etherification and esterification of cyclic ethers.

Resist Composition

The positive resist composition used in the pattern forming process comprises a base resin. A polymer comprising recurring units having lactone ring, specifically recurring units having 7-oxanorbornane ring, and preferably recurring units having the general formula (1) is useful as the base resin. The polymer having formula (1) is highly reactive in crosslinking reaction because both ester group and cyclic ether are contained in a common recurring unit. Since this unit also serves as an adhesive unit, advantageously the base resin is amenable to the pattern forming process without further incorporating additional units into the resin.

Herein R¹ is hydrogen or methyl. R² is a single bond, or a straight, branched or cyclic C₁-C₆ alkylene group which may have an ether or ester radical. When R² is alkylene, the alkylene has a primary or secondary carbon atom bonded to the ester group in the formula. R³, R⁴, and R⁵ are each hydrogen or a straight, branched or cyclic C₁-C₆ alkyl group. The subscript “a” is a number in the range: 0<a<1.0.

Exemplary C₁-C₆ alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, n-pentylene, isopentylene, cyclopentylene, n-hexylene, and cyclohexylene.

Exemplary C₁-C₆ alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, and cyclohexyl.

Those monomers Ma from which recurring units (a) having formula (1) are derived have the following formula wherein R¹ to R⁵ are as defined above.

Examples of monomers Ma are given below.

In the inventive process, once the first pattern is formed via exposure and development, deprotection of acid labile groups and crosslinkage are induced by the action of acid and heat. Then a film having an appropriate alkaline solubility (reversal film) is coated thereon and alkaline developed.

Subsequent to illumination and heating, the first pattern turns to a film which is alkaline soluble as a result of deprotection of acid labile groups in the acid labile group-containing recurring units and which is insoluble in a solvent (i.e., solvent in a reversal film-forming composition) as a result of crosslinking of 7-oxanorbornane ring. Thus, when a pattern reversal film-forming composition having a film-forming material dissolved in an organic solvent is coated on the first pattern, intermixing of the first pattern with the pattern reversal film-forming material is avoided.

The reversal film is then treated with an alkaline developer. When a surface portion of the reversal film is dissolved away to the level of the first pattern, dissolution of the first pattern starts. Image reversal occurs in this way.

When a polymer comprising recurring units having oxirane or oxetane is used as the base resin, it does not function as a positive resist composition as desired in the invention because the oxirane or oxetane ring has so high a rate of acid-assisted cleavage reaction that the polymer may undergo crosslinking at resist processing temperatures, for example, at 90 to 130° C. during PEB, and thus become alkali insoluble. In contrast, the 1,4-epoxy bond of 7-oxanorbornane ring is low reactive in acid-assisted cleavage reaction as compared with the oxirane or oxetane ring so that the polymer may not undergo crosslinking in the heating temperature range of PEB. Recurring units having 7-oxanorbornane ring are stable relative to acid in the course from coating to development and exert as a hydrophilic group a function of improving adhesion and alkaline solubility. However, under the impetus of the acid generated by flood exposure or heating of the developed pattern and heating at 170° C. or higher, ring opening of the 1,4-epoxy bond of 7-oxanorbornane ring occurs and crosslinking reaction takes place, leading to insolubility in the solvent. At the same time, deprotection of acid labile groups in the acid labile group-containing recurring units occurs under the impetus of acid and heat, leading to an increased alkaline solubility. For generating acid, a thermal acid generator may be added to the resist composition or the surface of the developed pattern may be subjected to flood exposure to UV having wavelength of less than 400 nm.

In the positive resist composition for use in the pattern forming process, a polymer comprising crosslinkable recurring units (a) having the general formula (1) above and acid labile group-containing recurring units (b) having the general formula (2) below is preferably used as the base resin.

Herein R⁶ is hydrogen or methyl, R⁷ is an acid labile group, and b is a number in the range: 0<b≦0.8.

Those monomers Mb from which recurring units (b) having formula (2) are derived have the following formula wherein R⁶ and R⁷ are as defined above.

The acid labile group represented by R⁷ in formula (2) may be selected from a variety of such groups, specifically groups of the following formulae (AL-10) and (AL-11), tertiary alkyl groups of the following formula (AL-12), and oxoalkyl groups of 4 to 20 carbon atoms, but not limited thereto.

In formulae (AL-10) and (AL-11), R⁵¹ and R⁵⁴ each are a monovalent hydrocarbon group, typically a straight, branched or cyclic alkyl group of 1 to 40 carbon atoms, more specifically 1 to 20 carbon atoms, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The subscript “a5” is an integer of 0 to 10, and especially 1 to 5. R⁵² and R⁵³ each are hydrogen or a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₂₀ alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R⁵² and R⁵³, R⁵² and R⁵⁴, or R⁵³ and R⁵⁴, taken together, may form a ring, specifically aliphatic ring, with the carbon atom or the carbon and oxygen atoms to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.

In formula (AL-12), R⁵⁵, R⁵⁶ and R⁵⁷ each are a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₂₀ alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively, a pair of R⁵⁵ and R⁵⁶, R⁵⁵ and R⁵⁷, or R⁵⁶ and R⁵⁷, taken together, may form a ring, specifically aliphatic ring, with the carbon atom to which they are attached, the ring having 3 to 20 carbon atoms, especially 4 to 16 carbon atoms.

Illustrative examples of the groups of formula (AL-10) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl and 2-tetrahydrofuranyloxycarbonylmethyl as well as substituent groups of the following formulae (AL-10)-1 to (AL-10)-10.

In formulae (AL-10)-1 to (AL-10)-10, R⁵⁸ is each independently a straight, branched or cyclic C₁-C₈ alkyl group, C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; R⁵⁹ is hydrogen or a straight, branched or cyclic C₁-C₂₀ alkyl group; R⁶⁰ is a C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; and “a5” is an integer of 0 to 10.

Illustrative examples of the acetal group of formula (AL-11) include those of the following formulae (AL-11)-1 to (AL-11)-34.

Other examples of acid labile groups include those of the following formula (AL-11a) or (AL-11b) while the polymer may be crosslinked within the molecule or between molecules with these acid labile groups.

Herein R⁶¹ and R⁶² each are hydrogen or a straight, branched or cyclic C₁-C₈ alkyl group, or R⁶¹ and R⁶², taken together, may form a ring with the carbon atom to which they are attached, and R⁶¹ and R⁶² are straight or branched C₁-C₈ alkylene groups when they form a ring. R⁶³ is a straight, branched or cyclic C₁-C₁₀ alkylene group. Each of b5 and d5 is 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. “A” is a (c5+1)-valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, which may be separated by a heteroatom such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, carbonyl groups or fluorine atoms. “B” is —CO—O—, —NHCO—O— or —NHCONH—.

Preferably, “A” is selected from divalent to tetravalent, straight, branched or cyclic C₁-C₂₀ alkylene, alkanetriyl and alkanetetrayl groups, and C₆-C₃₀ arylene groups, which may be separated by a heteroatom such as oxygen, sulfur or nitrogen or in which some of the hydrogen atoms attached to carbon atoms may be substituted by hydroxyl, carboxyl, acyl groups or halogen atoms. The subscript c5 is preferably an integer of 1 to 3.

The crosslinking acetal groups of formulae (AL-11a) and (AL-11b) are exemplified by the following formulae (AL-11)-35 through (AL-11)-42.

Illustrative examples of the tertiary alkyl of formula (AL-12) include tert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl, 1-ethylcyclopentyl, and tert-amyl groups as well as those of (AL-12)-1 to (AL-12)-16.

Herein R⁶⁴ is each independently a straight, branched or cyclic C₁-C₈ alkyl group, C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; R⁶⁵ and R⁶⁷ each are hydrogen or a straight, branched or cyclic C₁-C₂₀ alkyl group; and R⁶⁶ is a C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group.

With R⁶⁸ representative of a di- or poly-valent alkylene or arylene group included as shown in formulae (AL-12)-17 and (AL-12)-18, the polymer may be crosslinked within the molecule or between molecules. In formulae (AL-12)-17 and (AL-12)-18, R⁶⁴ is as defined above; R⁶⁸ is a straight, branched or cyclic C₁-C₂₀ alkylene group or arylene group, which may contain a heteroatom such as oxygen, sulfur or nitrogen; and b6 is an integer of 1 to 3.

The groups represented by R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ may contain a heteroatom such as oxygen, nitrogen or sulfur. Such groups are exemplified by those of the following formulae (AL-13)-1 to (AL-13)-7.

Of the acid labile groups of formula (AL-12), recurring units having an exo-form structure represented by the formula (AL-12)-19 are preferred.

Herein, R⁶⁹ is a straight, branched or cyclic C₁-C₈ alkyl group or a substituted or unsubstituted C₆-C₂₀ aryl group; R⁷⁰ to R⁷⁵, R⁷⁸ and R⁷⁹ are each independently hydrogen or a monovalent hydrocarbon group, typically alkyl, of 1 to 15 carbon atoms which may contain a heteroatom; and R⁷⁶ and R⁷⁷ are hydrogen. Alternatively, a pair of R⁷⁰ and R⁷¹, R⁷² and R⁷⁴, R⁷² and R⁷⁵, R⁷³ and R⁷⁵, R⁷³ and R⁷⁹, R⁷⁴ and R⁷⁸, R⁷⁶ and R⁷⁷, or R⁷⁷ and R⁷⁸, taken together, may form a ring, specifically aliphatic ring, with the carbon atom(s) to which they are attached, and in this case, each R is a divalent hydrocarbon group, typically alkylene, of 1 to 15 carbon atoms which may contain a heteroatom. Also, a pair of R⁷⁰ and R⁷⁹, R⁷⁶ and R⁷⁹, or R⁷² and R⁷⁴ which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.

The ester form monomers from which recurring units having an exo-form structure represented by the formula (AL-12)-19 are derived are described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633).

It is noted that R¹¹¹ and R¹¹² are each independently hydrogen, methyl, —COOCH₃, —CH₂COOCH₃ or the like. Illustrative non-limiting examples of suitable monomers are given below.

Also included in the acid labile groups of formula (AL-12) are acid labile groups having furandiyl, tetrahydrofurandiyl or oxanorbornanediyl as represented by the following formula (AL-12)-20.

Herein, R⁸⁰ and R⁸¹ are each independently a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₁₀ alkyl. R⁸⁰ and R⁸¹, taken together, may form an aliphatic hydrocarbon ring of 3 to 20 carbon atoms with the carbon atom to which they are attached. R⁸² is a divalent group selected from furandiyl, tetrahydrofurandiyl and oxanorbornanediyl. R⁸³ is hydrogen or a monovalent hydrocarbon group, typically a straight, branched or cyclic C₁-C₁₀ alkyl, which may contain a heteroatom.

Examples of the monomers from which the recurring units substituted with acid labile groups having furandiyl, tetrahydrofurandiyl and oxanorbornanediyl as represented by the formula:

(wherein R⁸⁰ to R⁸³, and R¹¹² are as defined above) are derived are shown below. Note that Me is methyl and Ac is acetyl.

While the polymer used herein preferably includes recurring units (a) of formula (1) and recurring units (b) of formula (2), it may have copolymerized therein recurring units (c) derived from monomers having adhesive groups such as hydroxy, cyano, carbonyl, ester, ether groups, lactone rings, carboxyl groups or carboxylic anhydride groups. Examples of monomers from which recurring units (c) are derived are given below.

Of the recurring units (c), those having an α-trifluoromethyl alcohol group or carboxyl group are preferably incorporated in copolymers because they improve the alkali dissolution rate of the developed pattern after heating. Examples of recurring units having a carboxyl group are given below.

In the polymer of the invention, the recurring units (a), (b) and (c) are present in proportions a, b, and c, respectively, which satisfy the range: 0<a<1.0, 0<b≦0.8, 0.1≦a+b≦1.0, 0≦c<1.0, and preferably the range: 0.1≦a≦0.9, 0.1≦b≦0.7, 0.2≦a+b≦1.0, and 0≦c≦0.9, provided that a+b+c=1.

It is noted that the meaning of a+b=1 is that in a polymer comprising recurring units (a) and (b), the sum of recurring units (a) and (b) is 100 mol % based on the total amount of entire recurring units. The meaning of a+b<1 is that the sum of recurring units (a) and (b) is less than 100 mol % based on the total amount of entire recurring units, indicating the inclusion of other recurring units, for example, units (c).

The polymer serving as the base resin in the resist material used in the pattern forming process of the invention should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000 to 30,000, as measured by GPC using polystyrene standards. With too low a Mw, the efficiency of thermal crosslinking in the resist material after development may become low. With too high a Mw, the polymer may lose alkaline solubility and have more likelihood of footing after pattern formation.

If a polymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that following exposure, foreign matter is left on the pattern or the pattern profile is exacerbated. The influences of molecular weight and dispersity become stronger as the pattern rule becomes finer. Therefore, the multi-component copolymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.

It is understood that a blend of two or more polymers which differ in compositional ratio, molecular weight or dispersity is acceptable.

The polymer as used herein may be synthesized by any desired method, for example, by dissolving unsaturated bond-containing monomers corresponding to the respective units (a), (b) and (c) in an organic solvent, adding a radical initiator thereto, and effecting heat polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran, diethyl ether and dioxane. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably the system is heated at 50 to 80° C. for polymerization to take place. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. The acid labile group that has been incorporated in the monomers may be kept as such, or the acid labile group may be once eliminated with an acid catalyst and thereafter protected or partially protected.

As described previously, the pattern forming process of the invention comprises the steps of coating the positive resist composition described above onto a substrate, prebaking the resist composition to form a resist film, exposing a selected area of the resist film to high-energy radiation, post-exposure baking, and developing the resist film with an alkaline developer to dissolve the exposed area thereof to form a resist pattern such as a dot pattern. The subsequent step is to treat the resist pattern (area unexposed to high-energy radiation) so as to generate an acid, thereby eliminating acid labile groups on the polymer (i.e., deprotection) and inducing crosslinking to the polymer in the resist pattern. In this deprotected and crosslinked state, the polymer has a dissolution rate in excess of 2 nm/sec, preferably of 3 to 5,000 nm/sec, and more preferably 4 to 4,000 nm/sec in an alkaline developer. It is preferred in attaining the objects of the invention that the dissolution rate of the polymer is higher than the dissolution rate of the reversal film (to be described later) in the same alkaline developer by a factor of 2 to 250,000, and especially 5 to 10,000.

In order that the polymer have a desired dissolution rate in the deprotected and crosslinked state, the polymer formulation is preferably designed such that the acid labile group-bearing recurring units (b) of formula (2) account for 10 mol % to 90 mol %, and more preferably 12 mol % to 80 mol % of the entire recurring units.

The resist composition used in the pattern forming process of the invention may further comprise an organic solvent, a compound capable of generating an acid in response to high-energy radiation (known as “acid generator”), and optionally, a dissolution regulator, a basic compound, a surfactant, and other components.

The resist composition used herein may include an acid generator in order for the composition to function as a chemically amplified positive resist composition. Typical of the acid generator used herein is a photoacid generator (PAG) capable of generating an acid in response to actinic light or radiation. The PAG may preferably be compounded in an amount of 0.5 to 30 parts and more preferably 1 to 20 parts by weight per 100 parts by weight of the base resin. The PAG is any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. The PAGs may be used alone or in admixture of two or more. Exemplary acid generators are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122] to [0142]).

The resist composition may further comprise one or more of an organic solvent, basic compound, dissolution regulator, surfactant, and acetylene alcohol. Their examples are described in JP-A 2008-111103. Specifically, exemplary organic solvents are described in paragraphs [0144] to [0145], exemplary basic compounds in paragraphs [0146] to [0164], and exemplary surfactants in paragraphs [0165] to [0166]. Exemplary dissolution regulators are described in JP-A 2008-122932 (US 2008090172), paragraphs [0155] to [0178], and exemplary acetylene alcohols in paragraphs [0179] to [0182]. The organic solvent may be added in an amount of 100 to 10,000 parts, and specifically 300 to 8,000 parts by weight per 100 parts by weight of the base resin. The basic compound may be added in an amount of 0.0001 to 30 parts, and specifically 0.001 to 20 parts by weight per 100 parts by weight of the base resin.

In an embodiment wherein a thermal acid generator in the form of an ammonium salt is added to the photoresist composition in an amount of 0.001 to 20 parts, preferably 0.01 to 10 parts by weight per 100 parts by weight of the base resin, an acid can be generated by heating. In this embodiment, acid generation, crosslinking reaction and deprotection reaction of acid labile groups proceed simultaneously. The preferred heating conditions include a temperature of 100 to 300° C., and especially 130 to 250° C., and a time of 10 to 300 seconds. This results in a resist film which meets the necessary properties for positive/negative reversal including alkaline solubility and solvent insolubility and has an increased mechanical strength sufficient to prevent deformation of the pattern by heating.

Suitable ammonium salts serving as the thermal acid generator include compounds of the formula (P1a-2).

Herein K⁻ is a sulfonate having at least one fluorine substituted at α-position, or perfluoroalkylimidate or perfluoroalkylmethidate. R^(101d), R^(101e), R^(101f), and R^(101g) are each independently hydrogen, a straight, branched or cyclic C₁-C₁₂ alkyl, alkenyl, oxoalkyl or oxoalkenyl group, a C₆-C₂₀ aryl group, or a C₁-C₁₂ aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups. Alternatively, R^(101d) and R^(101e), or R^(101d), R^(101e) and R^(101f) may bond together to form a ring with the nitrogen atom to which they are attached, and each of R^(101e) and R^(101f) or each of R^(101d), R^(101e) and R^(101f) is a C₃-C₁₀ alkylene group or a hetero-aromatic ring having incorporated therein the nitrogen atom when they form a ring.

Examples of K⁻ include perfluoroalkanesulfonates such as triflate and nonaflate, imidates such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and bis(perfluorobutylsulfonyl)imide, methidates such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide, and sulfonates having fluorine substituted at α-position, represented by the formula (K-1), and sulfonates having fluorine substituted at α-position, represented by the formula (K-2).

In formula (K-1), R¹⁰² is hydrogen, a straight, branched or cyclic C₁-C₂₀ alkyl or acyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl or aryloxy group, which may have an ether, ester, carbonyl radical or lactone ring and in which some or all hydrogen atoms may be substituted by fluorine atoms. In formula (K-2), R¹⁰³ is hydrogen, a straight, branched or cyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group.

In a further embodiment, a polymeric additive comprising recurring units having amino and fluoroalkyl groups may be added to the resist composition. The polymeric additive may be added in an amount of 0.01 to 20 parts, preferably 0.1 to 15 parts by weight per 100 parts by weight of the base resin. The polymeric additive segregates toward the resist film surface after coating for eventually preventing a resist pattern as developed from slimming and enhancing the rectangularity thereof. If a dot pattern as developed is slimmed or thinned, such slimming may interfere with image reversal. Addition of a polymer as shown below is effective for preventing the pattern film from slimming.

Herein, R⁰¹, R⁰⁴, and R⁰⁷ are each independently hydrogen or methyl. X₁, Y₁ and Y₂ are each independently a single bond, —O—R⁰⁹—, —C(═O)—O—R⁰⁹— or —C(═O)—NH—R⁰⁹—, straight or branched C₁-C₄ alkylene, or phenylene group. R⁰⁹ is a straight, branched or cyclic C₁-C₁₀ alkylene group, which may contain an ester (—COO—) or ether (—O—) radical. The subscript k is 1 or 2. In case of k=1, Y₁ is a single bond, —O—R⁰⁹—, —C(═O)—O—R⁰⁹— or —C(═O)—NH—R⁰⁹—, straight or branched C₁-C₄ alkylene, or phenylene group, wherein R⁰⁹ is as defined above. In case of k=2, Y₁ is —O—R¹⁰¹═, —C(═O)—O—R¹⁰¹═ or —C(═O)—NH—R¹⁰¹═, straight or branched C₁-C₄ alkylene group with one hydrogen eliminated, or phenylene group with one hydrogen eliminated, wherein R¹⁰¹ is a straight, branched or cyclic C₁-C₁₀ alkylene group with one hydrogen atom eliminated, which may contain an ester or ether radical. R⁰² and R⁰³ are each independently hydrogen, a straight, branched or cyclic C₁-C₂₀ alkyl group or C₂-C₂₀ alkenyl group which may contain a hydroxyl, ether, ester, cyano, amino radical, double bond, or halogen atom, or a C₆-C₁₀ aryl group. R⁰² and R⁰³ may bond together to form a C₃-C₂₀ ring with the nitrogen atom to which they are attached. R⁰⁵ is a straight, branched or cyclic C₁-C₁₂ alkylene group. R⁰⁶ is hydrogen, fluorine, methyl, trifluoromethyl or difluoromethyl, or R⁰⁶ may bond with R⁰⁵ to form a C₂-C₁₂ aliphatic ring with the carbon atom to which they are attached, which ring may contain an ether radical, fluorinated alkylene or trifluoromethyl radical. R⁰⁸ is a straight, branched or cyclic C₁-C₂₀ alkyl group which is substituted with at least one fluorine atom and which may contain an ether, ester or sulfonamide radical. The subscripts d, e-1, and e-2 are numbers in the range: 0<d<1.0, 0≦(e-1)<1.0, 0≦(e-2)<1.0, 0<(e-1)+(e-2)<1.0, and 0.5≦d+(e-1)+(e-2)≦1.0.

Reversal Film

On the other hand, the reversal film used has a dissolution rate of 0.02 nm/sec to 2 nm/sec, preferably 0.05 nm/sec to 1 nm/sec in an alkaline developer used in the reversal step of the inventive process. A dissolution rate of less than 0.02 nm/sec suggests that the reversal film may not be dissolved to the top level of the first resist pattern, resulting in a failure of pattern reversal or a surface layer of the reversed pattern becoming bulged. A dissolution rate of more than 2 nm/sec may lead to the disadvantage that the remaining reversal film is lessened or the hole size of the reversal pattern is enlarged.

In order that the film surface be adequately dissolved during development to form a trench pattern, the alkaline dissolution rate is controlled to a range of 0.05 nm/sec to 1 nm/sec. Outside the range, a faster dissolution rate may lead to a greater film slimming during development. At a slower dissolution rate, the film surface may not be dissolved, failing to configure a trench pattern. For the purpose of tailoring to an appropriate dissolution rate, units providing an alkaline dissolution rate of at least 1 nm/sec and units providing an alkaline dissolution rate of up to 0.05 nm/sec are copolymerized. Optimizing the copolymerization ratio leads to a material having an optimum dissolution rate.

The film (reversal film) used in the pattern forming process and having a dissolution rate of 0.02 nm/sec to 2 nm/sec in the alkaline developer may be formed of hydrocarbon base materials or silicon-containing materials. Preferably used are materials comprising polymers having phenolic hydroxyl, α-trifluoromethylhydroxyl and carboxyl groups as the base polymer. The preferred silicon-containing materials are those having silanol groups as well as the foregoing alkali soluble groups. Examples of the polymers having phenolic hydroxyl groups include cresol novolac resins, phenol oligomers, bisphenol oligomers, bisphenol novolac resins, bisnaphthol oligomers, bisnaphthol novolac resins, calixarene, calix resorcinol, polyhydroxystyrene, polyhydroxyvinylnaphthalene, polyhydroxyindene and copolymers thereof, carboxystyrene polymers, carboxyvinylnaphthalene and copolymers thereof, α-trifluoromethylhydroxy-containing styrene polymers and copolymers, methacrylic acid and carboxyl-containing (meth)acrylate polymers and copolymers, α-trifluoromethylhydroxy-containing (meth)acrylate polymers and copolymers.

Since most polymers consisting of recurring units having phenolic hydroxyl, α-trifluoromethylhydroxyl and carboxyl groups have an alkaline dissolution rate of at least 1 nm/sec, they are copolymerized with units providing an alkaline dissolution rate of up to 0.05 nm/sec. Examples of suitable units providing an alkaline dissolution rate of up to 0.05 nm/sec include those in which the hydrogen atom of phenolic hydroxyl, α-trifluoromethylhydroxyl or hydroxyl moiety of carboxyl group is replaced by a C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₆-C₂₀ aryl or acid labile group. Also included are styrene, indene, indole, chromone, coumarone, acenaphthylene, norbornadiene, norbornene, vinylnaphthalene, vinylanthracene, vinylcarbazole, vinyl ether derivatives, lactone-containing (meth)acrylates, and hydroxy-containing (meth)acrylates.

More specifically, reactants from which the polymer for use in the reversal film is prepared should have alkali soluble groups such as phenolic hydroxyl, α-trifluoromethylhydroxyl and carboxyl groups. Partial protection of alkali soluble groups or combination thereof with substantially alkali insoluble groups is sometimes necessary to tailor the alkaline dissolution rate.

Suitable polymers having a phenolic hydroxyl group include those novolac resins obtained by reaction of phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, pyrogallol, thymol, isothymol, or the like, in the presence of aldehydes. Polymers of polymerizable olefin compounds having a phenolic hydroxyl group include polymers of hydroxystyrene, hydroxyvinylnaphthalene, hydroxyvinylanthracene, hydroxyindene, hydroxyacenaphthylene, and the monomers shown below.

Polymers of monomers from which carboxyl-bearing recurring units are derived may also be used as the material for forming the reversal film. Examples of the monomers are shown below.

For partial protection of phenolic hydroxyl or carboxyl groups for the purpose of tailoring the alkaline dissolution rate, the hydrogen atom of the hydroxyl group or hydroxyl moiety of the carboxyl group is preferably replaced by a C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₆-C₂₀ aryl, acetyl, pivaloyl or acid labile group. The acid labile group used herein may be the same as described above.

For the purpose of tailoring the alkaline dissolution rate, substantially alkali insoluble recurring units (s-3) may also be copolymerized. Examples of the substantially alkali insoluble recurring units include recurring units derived from alkyl or aryl (meth)acrylates, hydroxyl or lactone-bearing (meth)acrylates, styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, vinylcarbazole, indene, acenaphthylene, norbornenes, norbornadienes, tricyclodecenes, and tetracyclododecenes.

The preferred base polymers from which the reversal film is formed are hydrocarbon polymers, especially polymers comprising aromatic group-bearing hydrocarbons.

As the silicon-containing material for use in the reversal film-forming composition, silicon polymers based on silsesquioxane are preferred from the standpoint of etch resistance.

The base polymer should preferably have a weight average molecular weight (Mw) of 1,000 to 200,000, and more preferably 1,500 to 100,000, as measured by GPC versus polystyrene standards. Also it should preferably have a dispersity (Mw/Mn) of 1.0 to 7.0, and more preferably 1.02 to 5.0.

In addition to the base polymer described above, the reversal film-forming composition may comprise a scarcely alkali soluble material for pattern reversal, an alkali soluble surfactant for enhancing a surface alkali dissolution rate, an alkali soluble etching resistance improver, a basic quencher, an organic solvent and the like.

Examples of the scarcely alkali soluble material for pattern reversal include fullerenes having phenol group or malonic acid substituted thereon and oligomeric phenol compounds. These materials have a high carbon content and the function of improving etching resistance as well. Pattern reversal materials may be used alone or in a blend of two or more.

Examples of suitable materials include the phenolic compounds described in JP-A 2006-259249, JP-A 2006-259482, JP-A 2006-285095, and JP-A 2006-293298, the bisnaphthol compounds described in JP-A 2007-199653, and fluorene compounds having a phenol group, including 4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-dimethyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-diallyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-difluoro-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-diphenyl-4,4′-(9H-fluoren-9-ylidene)bisphenol, 2,2′-dimethoxy-4,4′-(9H-fluoren-9-ylidene)bisphenol, tetrahydrospirobiindene compounds, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′,4,4′-hexamethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-5,5′-diol, 5,5′-dimethyl-3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, tritylphenol, etc. These materials may be used as the alkali soluble etching resistance improver.

The above material is preferably added in an amount of 0 to 200 parts, and more preferably 0 to 100 parts by weight per 100 parts by weight of the base polymer. When added, the amount of the material is at least 1 phr, and more preferably at least 5 phr.

Enhancing the alkali solubility of only a surface layer of the pattern reversal film is advantageous for smoothing dissolution of the pattern reversal film building up over the positive resist pattern which has been altered to be alkali soluble, and for enhancing the dimensional control of a trench pattern or hole pattern converted from the positive pattern. To enhance the surface alkali solubility, an alkali soluble surfactant, especially fluorochemical surfactant may be added. The preferred fluorochemical surfactants are those comprising either one or both of recurring units (s-1) and (s-2) represented by the general formula (3).

Herein, R⁸ and R¹¹ are each independently hydrogen or methyl. The letter n is equal to 1 or 2. In case of n=1, X₁ is a phenylene group, —O—, —C(═O)—O—R¹⁴—, or —C(═O)—NH—R¹⁴— wherein R¹⁴ is a single bond or a straight or branched C₁-C₄ alkylene group which may have an ester or ether radical. In case of n=2, X₁ is a phenylene group with one hydrogen atom eliminated (represented by —C₆H₃—), or —C(═O)—O—R⁸¹═ or —C(═O)—NH—R⁸¹═ wherein R⁸¹ is a straight, branched or cyclic C₁-C₁₀ alkylene group with one hydrogen atom eliminated, which may have an ester or ether radical. R⁹ is a single bond or a straight, branched or cyclic C₁-C₁₂ alkylene group. R¹⁰ is hydrogen, fluorine, methyl, trifluoromethyl or difluoromethyl, or R¹⁰ and R⁹ may bond together to form a ring of 3 to 10 carbon atoms (exclusive of aromatic ring) with the carbon atom to which they are attached, which ring may have an ether, fluorinated alkylene or trifluoromethyl radical. X₂ is a phenylene group, —O—, —C(═O)—O—R¹³—, or —C(═O)—NH—R¹³— wherein R¹³ is a single bond or a straight or branched C₁-C₄ alkylene group which may have an ester or ether radical. R¹² is fluorine or a straight, branched or cyclic C₁-C₂₀ alkyl group which is substituted with at least one fluorine atom and which may have an ether, ester or sulfonamide radical. The letter m is an integer of 1 to 5 when X₂ is phenylene, and m is 1 when X₂ is otherwise.

Examples of the monomers from which units (s-1) are derived are illustrated below.

Herein R⁸ is as defined above.

Examples of the monomers from which recurring units (s-2) in formula (3) are derived are illustrated below while many recurring units (s-2) are units having a fluorinated alkyl group.

Herein R¹¹ is as defined above.

These recurring units (s-1) and (s-2) may be copolymerized with the above-described alkali soluble recurring units having a phenol or carboxyl group or substantially alkali insoluble recurring units (s-3). In these copolymers, the proportion of recurring units (s-1) and (s-2) is 0≦(s-1)≦1, 0≦(s-2)≦1, and 0<(s-1)+(s-2)≦1, preferably 0.1<(s-1)+(s-2)≦1, and more preferably 0.2<(s-1)+(s-2)≦1. Understandably, in the case of (s-1)+(s-2)<1, the balance consists of recurring units (s-3) described above.

This alkali soluble surfactant should preferably have a weight average molecular weight (Mw) of 1,000 to 100,000 and more preferably 2,000 to 50,000.

The alkali soluble surfactant is preferably added in an amount of 0 to 50 parts, and more preferably 0 to 20 parts by weight per 100 parts by weight of the base polymer. Too much amounts of the surfactant may cause excessive film slimming or detract from etching resistance. When added, at least 1 phr of the surfactant is preferred.

The basic quencher used herein may be any of the same basic compounds as described in conjunction with the positive resist composition. Specifically, a basic compound may be added to the pattern reversal film used in the pattern forming process of the invention for preventing acid diffusion from the resist pattern as developed. Particularly when an acid labile group-substituted phenolic compound or carboxyl-containing compound is used as the component of the pattern reversal film, there arises the problem that the alkali dissolution rate increases due to diffusion of acid from the resist pattern and deprotection reaction, leading to the reversal pattern of an increased size or substantially reduced thickness. This problem is effectively overcome by adding a basic compound. Understandably the basic compounds added to the resist composition and the pattern reversal film composition may be the same or different.

The basic compound or basic quencher is preferably added in an amount of 0 to 10 parts, and more preferably 0 to 5 parts by weight per 100 parts by weight of the base polymer. When added, at least 0.1 phr of the quencher is preferred.

To the reversal film-forming composition, an onium salt acid generator may be added. When an onium salt is added to a reversal film-forming composition comprising a phenol base material as the base polymer, the composition has a reduced alkali dissolution rate due to the dissolution-inhibiting effect of the onium salt. The addition of an onium salt is effective for tailoring the alkali dissolution rate.

In the pattern reversal film-forming composition used in the pattern forming process of the invention, the organic solvent used may be selected from those used in the positive resist composition, and from alcohols of 3 to 10 carbon atoms and ethers of 8 to 12 carbon atoms which are favorable in preventing mixing with the positive resist coating (i.e., resist pattern). Illustrative examples of the C₃-C₁₀ alcohols include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.

Examples of the C₈-C₁₂ ethers include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-t-amyl ether, and di-n-hexyl ether. These solvents may be used alone or in admixture of two or more. An aromatic solvent such as toluene, xylene or anisole may be mixed with the foregoing solvent.

The amount of the organic solvent used is preferably 200 to 3,000 parts, and more preferably 400 to 2,000 parts by weight per 100 parts by weight of the base polymer.

Process

Now referring to the drawings, the pattern forming process of the invention is illustrated. First, the positive resist composition is coated on a substrate to form a resist film thereon. As shown in FIG. 4A, a resist film 30 of a positive resist composition is formed on a processable substrate 20 disposed on a substrate 10 directly or via an intermediate intervening layer (not shown). The resist film preferably has a thickness of 10 to 1,000 nm and more preferably 20 to 500 nm. Prior to exposure, the resist film is heated or prebaked, preferably at a temperature of 60 to 180° C., especially 70 to 150° C. for a time of 10 to 300 seconds, especially 15 to 200 seconds.

The substrate 10 used herein is generally a silicon substrate. The processable substrate (or target film) 20 used herein includes SiO₂, SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, low dielectric film, and etch stopper film. The intermediate intervening layer includes hard masks of SiO₂, SiN, SiON or p-Si, an undercoat in the form of carbon film, a silicon-containing intermediate film, and an organic antireflective coating.

Suitable spin-on carbon films include nortricyclene copolymers described in JP-A 2004-205658, hydrogenated naphthol novolac resins described in JP-A 2004-205676, naphthol dicyclopentadiene copolymers described in JP-A 2004-205685, phenol dicyclopentadiene copolymers described in JP-A 2004-354554 and JP-A 2005-010431, fluorene bisphenol novolac described in JP-A 2005-128509, acenaphthylene copolymers described in JP-A 2005-250434, indene copolymers described in JP-A 2006-053543, phenol group-containing fullerene described in JP-A 2006-227391, bisphenol compounds and novolac resins thereof described in JP-A 2006-259249, JP-A 2006-293298, and JP-A 2007-316282, bisphenol compounds and novolac resins thereof described in JP-A 2006-259482, novolac resins of adamantane phenol compounds described in JP-A 2006-285095, hydroxyvinylnaphthalene copolymers described in JP-A 2007-171895, bisnaphthol compounds and novolac resins thereof described in JP-A 2007-199653, ROMP polymers described in JP-A 2008-26600, and tricyclopentadiene copolymers described in JP-A 2008-96684, and other resinous compounds.

The spin-on silicon-containing intermediate layers are preferably those layers comprising silsesquioxane-based silicon compounds and having an antireflection function as described in JP-A 2004-310019, JP-A 2005-15779, JP-A 2005-18054, JP-A 2005-352104, JP-A 2007-65161, JP-A 2007-163846, JP-A 2007-226170, and JP-A 2007-226204.

Where the reversal film is formed of a hydrocarbon base material, a carbon film having a carbon content of at least 75% by weight on the processable substrate and a silicon-containing intermediate layer thereon are preferably disposed between the processable substrate and the photoresist film for positive/negative reversal to construct a film stack suited for the three-layer resist process. The carbon film may be formed by spin coating or an amorphous carbon film formed by CVD. The silicon-containing intermediate layer may be a SOG film formed by spin coating or a film selected from SiO₂, SiN, SiON and TiN films formed by CVD or ALD, and has both functions of a hard mask for the carbon film and an antireflection film.

Also, an organic antireflective coating may be formed between the silicon-containing film and the photoresist film for the purposes of preventing footing on the substrate and pattern collapse and further reducing substrate reflection.

Where the reversal film is formed of a silicon-containing material, a carbon film having a carbon content of at least 75% by weight is formed between the processable substrate and the photoresist film for positive/negative reversal, and a photoresist film is formed thereon. An organic antireflective coating may be formed between the carbon film and the photoresist film. In this embodiment, the silicon-containing reversal film functions as a hard mask during processing of the carbon film.

This is followed by exposure. For the exposure, preference is given to high-energy radiation having a wavelength of 140 to 250 nm, and especially ArF excimer laser radiation of 193 nm. The exposure may be done either in air or in a dry atmosphere with a nitrogen stream, or by immersion lithography in water. The ArF immersion lithography uses deionized water or liquids having a refractive index of at least 1 and highly transparent to the exposure wavelength such as alkanes as the immersion solvent. The immersion lithography involves prebaking a resist film and exposing the resist film to light through a projection lens, with water introduced between the resist film and the projection lens. Since this allows lenses to be designed to a NA of 1.0 or higher, formation of finer feature size patterns is possible. The immersion lithography is important for the ArF lithography to survive to the 45-nm node. In the case of immersion lithography, deionized water rinsing (or post-soaking) may be carried out after exposure for removing water droplets left on the resist film, or a protective film may be applied onto the resist film after pre-baking for preventing any leach-out from the resist film and improving water slip on the film surface.

The resist protective film used in the immersion lithography is preferably formed from a solution of a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol residues which is insoluble in water, but soluble in an alkaline developer liquid, in a solvent selected from alcohols of at least 4 carbon atoms, ethers of 8 to 12 carbon atoms, and mixtures thereof. The protective coating composition used herein may comprise a base resin comprising predominant recurring units (P-1) such as recurring units having 1,1,1,3,3,3-hexafluoro-2-propanol residues or a base resin comprising the predominant recurring units (P-1) and recurring units (P-2) having a fluoroalkyl group copolymerized therewith. Examples of recurring units (P-1) include those derived from the monomers exemplified above for units (s-1), and examples of recurring units (P-2) include those derived from the monomers exemplified above for units (s-2). The proportion of these recurring units (P-1) and (P-2) is 0<(P-1)≦1.0, 0≦(P-2)<1.0, and 0.3≦(P-1)+(P-2)≦1.0. The base resin has a weight average molecular weight (Mw) of 1,000 to 100,000, and preferably 2,000 to 50,000. When a base resin free of recurring units (P-2) is used, it is preferred to incorporate an amine compound in the protective coating composition. The amine compound used herein may be selected from those described above in conjunction with the basic compound. The amine compound is preferably used in an amount of 0.01 to 10 parts, and more preferably 0.02 to 8 parts by weight per 100 parts by weight of the base resin.

After formation of the photoresist film, deionized water rinsing (or post-soaking) may be carried out for extracting the acid generator and the like from the film surface or washing away particles, or after exposure, rinsing (or post-soaking) may be carried out for removing water droplets left on the resist film.

Exposure is preferably carried out so as to provide an exposure dose of about 1 to 200 mJ/cm², more preferably about 10 to 100 mJ/cm². This is followed by baking (PEB) on a hot plate at 60 to 150° C. for 1 to 5 minutes, preferably at 80 to 120° C. for 1 to 3 minutes.

Thereafter the resist film is developed with a developer in the form of an aqueous alkaline solution, for example, an aqueous solution of 0.1 to 5 wt %, preferably 2 to 3 wt % TMAH for 0.1 to 3 minutes, preferably 0.5 to 2 minutes by conventional techniques such as dip, puddle or spray techniques. In this way, a desired resist pattern 30 a is formed on the substrate as shown in FIG. 4B.

As to the pattern, a dot pattern having a half-pitch size of 38×38 nm to 100×100 nm, and especially 40×40 nm to 80×80 nm may be formed using a lattice-like pattern mask. Since the size of a dot pattern depends on the lens NA of an exposure tool, use of an NA 1.35 exposure tool enables formation of dots having a half-pitch of 38 nm as the minimum size. The dots may have longitudinal and transverse axes of equal or different length. The method of forming a dot pattern is not particularly limited. A typical method of forming a dot pattern is by exposing the resist film to high-energy radiation through a lattice-like pattern phase shift mask and developing to form a dot pattern. With this method, holes having the finest half-pitch can be formed.

In the prior art, an attempt to form a dot pattern having such a fine pitch required two exposures through two masks by double dipole lithography. Specifically, the method includes a first exposure of X direction lines by dipole illumination, exchange of a mask, and a second exposure of Y direction lines by dipole illumination. In this case, throughput drops due to mask exchange and alignment associated therewith. Also, any misalignment between the two exposures leads to a positional shift of finally formed holes. If the position of a hole differs from the position of a line to be connected thereto, this causes a failure of interconnection. Thus the double dipole illumination method requires a very high accuracy of alignment.

In contrast to the fact that the pattern formed by two exposures by double dipole illumination suffers from misalignment of the second exposure, the pattern forming process of the invention is devoid of misalignment because only a single exposure is necessary. Because of no mask exchange and the only one exposure, there is an advantage of high throughput.

Next, PEB and development are carried out to form a dot pattern. A random pitch dot pattern may be formed through a single development (see FIG. 4B).

Next, the resist pattern is treated to eliminate acid labile groups in the polymer (base resin) in the pattern and to crosslink the polymer, forming a crosslinked pattern 30 b (FIG. 4C). To induce elimination of acid labile groups and crosslinking on the polymer in the resist pattern, acid and heat are necessary. In practice, once an acid is generated, heat is applied to effect elimination or deprotection of acid labile groups and crosslinking at the same time. The acid may be generated by a suitable method such as flood exposure of the wafer (pattern) as developed for decomposing the photoacid generator. The flood exposure uses an illumination wavelength of 180 to 400 nm and an exposure dose of 10 mJ/cm² to 1 J/cm². Radiation with a wavelength of less than 180 nm, specifically irradiation of excimer lasers or excimer lamps of 172 nm, 146 nm and 122 nm is undesirable because not only the generation of acid from photoacid generator, but also photo-induced crosslinking reaction are accelerated, leading to a decrease of alkaline dissolution rate due to exaggerated crosslinking. For the flood exposure, use is preferably made of an ArF excimer laser with a wavelength of 193 nm or more, a KrCl excimer lamp of 222 nm, a KrF excimer laser of 248 nm, a low-pressure mercury lamp centering at 254 nm, a XeCl excimer lamp of 308 nm, and i-line of 365 nm. In an alternative embodiment wherein a thermal acid generator in the form of an ammonium salt is added to the positive resist composition, the acid can be generated by heating. In this embodiment, acid generation and crosslinking reaction take place simultaneously. Preferred heating conditions include a temperature of 150 to 400° C., especially 160 to 300° C. and a time of 10 to 300 seconds. As a result, a crosslinked resist pattern which is insoluble in the solvent of the reversal film-forming composition is yielded. Since an additional illumination system is necessary to generate the acid by illumination, the latter embodiment is more advantageous that uses a resist composition having a thermal acid generator added thereto so that deprotection and crosslinking reaction may be driven only by heating.

Next, as shown in FIG. 4D, the reversal film-forming composition is built up until it covers the crosslinked resist pattern 30 b, forming a reversal film 40. Preferably the thickness of the reversal film 40 is equal to the height of the resist pattern 30 b or ±30 nm.

Next, the liquid alkaline developer is applied to dissolve a surface layer of the reversal film 40 until the crosslinked resist pattern 30 b is exposed. From this point of time downward, the crosslinked resist pattern 30 b is selectively dissolved since the dissolution rate in the alkaline developer of the crosslinked resist pattern 30 b is substantially higher than that of the reversal film 40. Eventually, the crosslinked resist pattern 30 b is dissolved away, yielding the reversal film 40 provided with a reversal pattern 40 a which is a negative of the crosslinked resist pattern 30 b as shown in FIG. 4E. If the resist pattern is a dot pattern, the resulting reversal pattern is a hole pattern.

The hole pattern printed as the reversal pattern may be shrunk by baking. That is, the size of holes may be reduced by baking. The baking is preferably at a temperature of 70 to 180° C., preferably 80 to 170° C. for a time of 10 to 300 seconds.

In another embodiment, the hole pattern printed as the reversal pattern may be shrunk by the RELACS method. Specifically, a shrinking agent is coated on the hole pattern and the structure is baked for shrinking the hole pattern. Useful materials are described in JP 3071401, JP-A 2001-228616, JP-A 2004-86203, JP-A 2004-294992, JP-A 2007-206728, and WO 2005/008340.

Typically a composition comprising a base polymer and the above-mentioned crosslinker in water or alcohol may be used as the shrinking agent. The base polymer is selected from among polyacrylic acid, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, polyethylene imine, polyethylene oxide, polyvinylamine, polyallylamine, styrene-maleic acid copolymers, poly(N-vinylformamide), polyoxazoline, melamine resins, urea resins, alkyd resins, and water-soluble resins based on sulfonamide or carbonamide.

A shrinking agent is coated on the hole pattern and baked so that the shrinking agent is attached to the reversed film. The baking is preferably at a temperature of 70 to 180° C., preferably 80 to 150° C. for a time of 10 to 300 seconds. Then the extra shrinking agent may be removed using water, alcohol, alkaline developer or a mixture thereof.

When a phenol base material is used as the reversal film in the pattern forming process, advantageously the pattern is amenable to shrinkage by the thermal flow and RELACS methods. A positive resist composition comprising a phenol base material forms a film having a glass transition temperature (Tg) which varies between dense and isolated hole patterns due to the difference in partial elimination amount of acid labile groups therebetween. The dense hole pattern is largely affected by fog light so that more partial deprotection takes place than in the isolated hole pattern, leading to a higher Tg. This reduces the quantity of deformation by flow and hence the shrinkage of holes. The reversal film material used in the pattern forming process is free of a difference in Tg of film between dense and isolated hole patterns because it does not resort to pattern formation by light exposure. This provides the advantage that there is no difference in shrinkage between dense and isolated holes.

Furthermore, as shown in FIG. 4F, using the reversal pattern 40 a as a mask, the intermediate intervening layer of hard mask or the like (if any) is etched, and the processable substrate 20 further etched. For etching of the intermediate intervening layer of hard mask or the like, dry etching with fluorocarbon or halogen gases may be used. For etching of the processable substrate, the etching gas and conditions may be properly chosen so as to establish an etching selectivity relative to the hard mask, and specifically, dry etching with fluorocarbon, halogen, oxygen, hydrogen or similar gases may be used. Thereafter, second resist film is removed. Removal of the film may be carried out after etching of the intermediate intervening layer of hard mask or the like. It is noted that removal of the second resist film may be achieved by dry etching with oxygen or radicals and removal of the second resist film may be achieved as previously described, or using strippers such as amines, sulfuric acid/aqueous hydrogen peroxide or organic solvents.

EXAMPLE

Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation “pbw” is parts by weight. For all polymers, Mw and Mn are determined by GPC versus polystyrene standards.

Synthesis Examples

A polymer for use in a reversal film-forming composition was prepared by combining monomers, effecting copolymerization reaction in tetrahydrofuran medium, crystallization in methanol, repeatedly washing with hexane, isolation, and drying. The resulting polymer (Polymer 1) had the composition shown below. Notably, a phenol group on a monomer was substituted by an acetoxy group, which was converted back to a phenol group by alkaline hydrolysis after polymerization. The composition of the polymer was analyzed by ¹H-NMR, and the Mw and Mw/Mn determined by GPC.

Polymer 1

-   -   Mw=9,300     -   Mw/Mn=1.88

A reversal film-forming composition was prepared by combining Polymer 1, a basic compound, and a solvent in accordance with the formulation of Table 1. To the solvent, 100 ppm of a fluorochemical surfactant FC-4430 (3M-Sumitomo Co., Ltd.) was added. The reversal film-forming composition was coated onto a HMDS-primed 8-inch silicon substrate and baked at 110° C. for 60 seconds to form a pattern reversal film (IROC-1) of 60 nm thick. The film was developed with a developer in the form of a 2.38 wt % TMAH aqueous solution for 30 seconds. A film thickness reduction by development was determined, from which a dissolution rate (in nm/s) was computed. The result is shown in Table 1.

-   Basic compound: Basic quencher 1 of the following structural formula

-   Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

TABLE 1 Pattern reversal film-forming composition Dissolution Reversal Polymer Additive Solvent rate film (pbw) (pbw) (pbw) (nm/s) IROC-1 Polymer 1 Basic PGMEA 0.2 (100) quencher 1 (3,000) (2.0)

Preparation of Positive Resist Composition and Alkali-Soluble Protective Coating Composition

A resist solution and a protective coating solution were prepared by dissolving polymers (Resist polymer and Protective film polymer) and components in solvents in accordance with the formulation of Tables 2 and 3, and filtering through a filter with a pore size of 0.2 μm. The components in Tables 2 and 3 are identified below.

-   Photoacid generator: PAG1 of the following structural formula

Resist Polymer 1

-   -   Mw=8,310     -   Mw/Mn=1.73

Protective Film Polymer

-   -   Mw=8,800     -   Mw/Mn=1.69

-   Basic compound: Basic quencher 2 of the following structural formula

Thermal Acid Generator:

-   -   TAG1 of the following structural formula

-   Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

TABLE 2 Acid Basic Organic Polymer generator compound solvent (pbw) (pbw) (pbw) (pbw) Resist 1 Resist PAG1 (12.0) Basic PGMEA Polymer 1 TAG1 (0.5) quencher 2 (2,000) (100) (1.20)

TABLE 3 Polymer Additive Organic solvent (pbw) (pbw) (pbw) TC-1 Protective tri-n-octylamine diisoamyl ether (2,700) Film Polymer (0.3) 2-methyl-1-butanol (270) (100) Film Thickness Change in Solvent and Alkali Dissolution Rate after High-Temperature Baking

On a substrate (silicon wafer), the resist composition prepared in accordance with the formulation of Table 2 was spin coated and baked on a hot plate at 190° C. for 60 seconds to form a resist film of 150 nm thick.

A solvent was statically dispensed on the resist film for 30 seconds. Thereafter, the sample was rotated at 2000 rpm for 30 seconds for spinning off the solvent and baked at 100° C. for 60 seconds for drying off the solvent. A film thickness was measured using a film thickness gauge, and a change of film thickness from the film as baked at 190° C. was computed.

Separately, the resist film as baked at 190° C. was examined for alkaline dissolution rate. Using a resist development analyzer RDA-790 (Lithotec Japan Co., Ltd.), an alkaline dissolution rate of the film in 2.38 wt % TMAH aqueous solution was measured. The results are shown in Table 4.

TABLE 4 Film slimming by solvent Alkali dissolution rate Solvent (nm) (nm/s) Resist 1 PGMEA 0.5 170

Examples 1, 2 and Comparative Examples 1, 2 ArF Lithography Patterning

On a substrate (silicon wafer), a spin-on carbon film ODL-50 (Shin-Etsu Chemical Co., Ltd.) having a carbon content of 80 wt % was deposited to a thickness of 200 nm and a silicon-containing spin-on hard mask SHB-A941 having a silicon content of 43 wt % was deposited thereon to a thickness of 35 nm. On this substrate for trilayer process, the resist composition shown in Table 2 was spin coated, then baked on a hot plate at 100° C. for 60 seconds to form a resist film of 100 nm thick. The protective coating composition TC-1 shown in Table 3 was spin coated on the resist film and baked at 90° C. for 60 seconds to form a protective film of 50 nm thick.

In Example 1, using an ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, 0.98/0.78, cross pole opening 20 deg., azimuthally polarized illumination), exposure was performed through a 6% halftone phase shift mask having the layout and dimensions shown in FIG. 34. After the exposure, the sample was baked (PEB) at 100° C. for 60 seconds and developed with a 2.38 wt % TMAH aqueous solution for 30 seconds.

Example 2 used the same film construction and mask as in Example 1. Using an ArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp., NA 1.30, a 0.98/0.78, dipole opening 20 deg., azimuthally polarized illumination), two exposures of X-direction dipole illumination and Y-direction dipole illumination were successively performed. After the exposure, the sample was baked (PEB) at 100° C. for 60 seconds and developed with a 2.38 wt % TMAH aqueous solution for 30 seconds.

Comparative Example 1 used the same film construction and exposure tool as in Example 1. Exposure was performed through the mask of FIG. 35 under conditions: NA 1.30, a 0.98/0.78, cross-pole opening 20 deg., and azimuthally polarized illumination. After the exposure, the sample was similarly processed.

By observation under TDSEM S-9380 (Hitachi Hitechnologies Ltd.), the size of dots as developed, dots as heated, and holes as image reversed was measured. The dots observed correspond to locations A-1, B-1, C-1 and D-1 on the mask of FIG. 34 in Examples 1 and 2, and locations A-2, B-2, C-2 and D-2 on the mask of FIG. 35 in Comparative Example 1. The results are shown in Table 5.

Comparative Example 2 used the same film construction and exposure tool as in Example 1. Hole pattern exposure was performed through a lattice-like mask with the layout of FIG. 15 having a pitch of 90 nm and a line width of 25 mm (or a hole size of 65 nm). After the exposure, the sample was baked (PEB) at 100° C. for 60 seconds and developed with a 2.38 wt % TMAH aqueous solution for 30 seconds. By observation under TDSEM S-9380 (Hitachi Hitechnologies Ltd.), the size of holes was measured. The minimum size of holes resolved was 50 nm while holes of smaller size could not be resolved.

TABLE 5 Results of reversal from dot pattern to hole pattern (size in nm) After development After baking After reversal A-1 B-1 C-1 D-1 A-1 B-1 C-1 D-1 A-1 B-1 C-1 D-1 Example 1 32 31 30 30 31 31 30 29 32 33 32 32 Example 2 33 33 33 32 34 34 33 30 35 35 36 34 After development After baking After reversal A-2 B-2 C-2 D-2 A-2 B-2 C-2 D-2 A-2 B-2 C-2 D-2 Comparative 30 25 15 12 31 24 12 10 not reversed Example 1

It is evident from Table 5 that in the pattern forming process of Example 1, 30-nm hole patterns including 1:1 dense holes at a pitch of 90 nm and isolated holes were opened through a single exposure. In Example 2, 30-nm hole patterns including 1:1 dense holes at a pitch of 90 nm and isolated holes were opened through two double dipole illumination exposures. By contrast, the prior art process of Comparative Example 1 failed to open hole patterns after reversal operation, because a substantial size difference arose between dense and isolated patterns and the dot pattern after development experienced a film slimming. In the attempt to resolve holes at a pitch of 90 nm through exposure and development in accordance with the prior art process, the smallest holes had a size of 50 nm.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Japanese Patent Application No. 2009-030281 is incorporated herein by reference.

Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. 

1. A process for forming a pattern by way of positive/negative reversal, comprising the steps of: coating a chemically amplified positive resist composition onto a processable substrate, the resist composition comprising a resin comprising recurring units of structure having acid labile groups which are eliminatable with acid, the resin turning to be soluble in an alkaline developer as a result of elimination of the acid labile groups, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and optionally, a thermal acid generator capable of generating an acid upon heating, and an organic solvent, prebaking the coating to remove the unnecessary solvent and to form a resist film, exposing the resist film to high-energy radiation through a phase shift mask including a lattice-like first shifter having a line width equal to or less than half a pitch and a second shifter arrayed on the first shifter and consisting of lines whose on-wafer size is 2 to 30 nm thicker than the line width of the first shifter, post-exposure baking so that the acid generated by the acid generator upon exposure may act on acid labile groups in the resin for thereby effecting elimination reaction of acid labile groups in the resin in exposed areas, developing the exposed resist film with an alkaline developer to form a positive pattern, illuminating or heating the positive pattern, the acid generated by illumination or the heat serving to eliminate acid labile groups in the resin in the positive pattern for thereby increasing the alkaline solubility of the resin and to induce crosslinks in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent used in a reversal film-forming composition, coating a reversal film-forming composition on the positive pattern-bearing substrate to form a reversal film, and dissolving away the crosslinked positive pattern using an alkaline wet etchant.
 2. The process of claim 1 wherein the second shifter is arrayed on the first shifter.
 3. The process of claim 1 wherein the second shifter is of crisscross or lattice-like shape.
 4. The process of claim 1 wherein the step of developing the exposed resist film is to form a pattern of dots only at the intersections between gratings of the second shifter.
 5. The process of claim 1 wherein the lattice-like first shifter is a halftone phase shift mask having a transmittance of 3 to 15%.
 6. The process of claim 1 wherein the phase shift mask includes the first shifter having a line width equal to or less than ⅓ of the pitch and the second shifter consisting of lines whose on-wafer size is 2 to 30 nm thicker than the line width of the first shifter.
 7. The process of claim 1 wherein in the step of illuminating or heating the positive pattern for increasing the alkaline solubility of the resin and for endowing the positive pattern with resistance to an organic solvent used in a reversal film-forming composition, the dissolution rate of the crosslinked positive pattern in an alkaline wet etchant is such that the crosslinked positive pattern exhibits an etching rate in excess of 2 nm/sec when etched with 2.38 wt % TMAH aqueous solution, the organic solvent used in the reversal film-forming composition is selected from the group consisting of propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and heptanone, and mixtures of two or more of the foregoing, the resistance to organic solvent of the crosslinked positive pattern is such that the crosslinked positive pattern experiences a film slimming of up to 10 nm when contacted with the organic solvent for 30 seconds.
 8. The process of claim 1 wherein said reversal film-forming composition comprises a resin comprising monomeric units of aromatic or alicyclic structure.
 9. The process of claim 1, further comprising, between the step of coating a reversal film-forming composition on the positive pattern-bearing substrate to form a reversal film and the step of dissolving away the crosslinked positive pattern using an alkaline wet etchant, the step of removing the reversal film deposited on the crosslinked positive pattern.
 10. The process of claim 9 wherein the step of removing the reversal film deposited on the crosslinked positive pattern includes wet etching.
 11. The process of claim 10 wherein the reversal film is soluble in an alkaline wet etchant, but has a dissolution rate which is slower than that of the crosslinked positive pattern after the step of endowing the positive pattern with resistance to organic solvent, the wet etching uses an alkaline wet etchant, and the step of removing the reversal film deposited on the crosslinked positive pattern and the step of dissolving away the crosslinked positive pattern are concurrently carried out.
 12. The process of claim 11 wherein the reversal film has a dissolution rate of 0.02 nm/sec to 2 nm/sec when etched with 2.38 wt % TMAH aqueous solution.
 13. The process of claim 1 wherein said chemically amplified positive resist composition comprises a component capable of generating an acid in the step of heating for endowing the positive pattern with organic solvent resistance.
 14. The process of claim 13 wherein the component capable of generating an acid is a thermal acid generator which is added to the resist composition in addition to the photoacid generator.
 15. The process of claim 14 wherein the thermal acid generator has the general formula (P1a-2):

wherein R^(101d), R^(101e), R^(101f), and R^(101g) are each independently hydrogen, a straight, branched or cyclic C₁-C₁₂ alkyl, alkenyl, oxoalkyl or oxoalkenyl group, a C₆-C₂₀ aryl group, or a C₇-C₁₂ aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups, or R^(101d) and R^(101e), or R^(101d), R^(101e) and R^(101f) may bond together to form a ring with the nitrogen atom to which they are attached, each of R^(101e) and R^(101f) or each of R^(101d), R^(101e) and R^(101f) is a C₃-C₁₀ alkylene group or a hetero-aromatic ring having incorporated therein the nitrogen atom when they form a ring, and K⁻ is a sulfonate having at least one α-position fluorinated, perfluoroalkylimidate or perfluoroalkylmethidate.
 16. The process of claim 1 wherein in said chemically amplified positive resist composition, the resin comprises recurring units having a lactone ring and recurring units having an acid labile group which is eliminatable with acid.
 17. The process of claim 1 wherein in said chemically amplified positive resist composition, the resin comprises an electrophilic partial structure such as an ester group or cyclic ether which will form crosslinks in the resin of the positive resist pattern.
 18. The process of claim 17 wherein in said chemically amplified positive resist composition, the resin comprises recurring units having a 7-oxanorbornane ring and recurring units having an acid labile group which is eliminatable with acid, and heat is applied in the step of illuminating the positive pattern to generate an acid whereby elimination of acid labile groups and crosslinking of the resin take place simultaneously in the positive pattern.
 19. The process of claim 18 wherein the recurring units having a 7-oxanorbornane ring are recurring units (a) having the general formula (1):

wherein R¹ is hydrogen or methyl, R² is a single bond or a straight, branched or cyclic C₁-C₆ alkylene group which may have an ether or ester radical, and which has a primary or secondary carbon atom through which it is linked to the ester group in the formula, R³, R⁴, and R⁵ are each independently hydrogen or a straight, branched or cyclic C₁-C₆ alkyl group, and “a” is a number in the range: 0<a<1.0.
 20. The process of claim 16 wherein the recurring units having an acid labile group which is eliminatable with acid are recurring units (b) having the general formula (2):

wherein R⁶ is hydrogen or methyl, R⁷ is an acid labile group, and b is a number in the range: 0<b≦0.8.
 21. The process of claim 20 wherein the acid labile group of R⁷ is an acid labile group of alicyclic structure which is eliminatable with acid.
 22. The process of claim 1 wherein the positive pattern comprises a dot pattern, and the pattern resulting from positive/negative reversal comprises a hole pattern.
 23. The process of claim 1 wherein the positive pattern comprises both a dense dot pattern and an isolated dot pattern, and the pattern resulting from positive/negative reversal comprises both a dense hole pattern and an isolated hole pattern.
 24. The process of claim 23 wherein a dense dot pattern and an isolated dot pattern are formed as the positive pattern by exposure to a dense dot pattern and subsequent exposure to an unnecessary portion of the dot pattern, and a dense hole pattern and an isolated hole pattern are formed by positive/negative reversal therefrom.
 25. A process for forming a pattern by way of positive/negative reversal according to claim 1, comprising the steps of: coating a chemically amplified positive resist composition onto a processable substrate, said resist composition comprising a resin comprising recurring units having acid labile groups which are eliminatable with acid, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and a solvent, heating to remove the unnecessary solvent to form a resist film, coating a protective film-forming composition onto the resist film and drying to form a protective film, exposing the resist film to high-energy radiation in a repeating dense pattern from a projection lens, by immersion lithography with water or a transparent liquid having a refractive index of at least 1 intervening between the resist film and the projection lens, further exposing an unnecessary region of the dense pattern or unexposed area by immersion lithography, post-exposure baking for causing the acid generated by the acid generator upon exposure to act on the acid labile groups on the resin whereby the acid labile groups on the resin in the exposed area undergo elimination reaction, and developing the exposed resist film with an alkaline developer to form a positive pattern, treating the positive pattern so as to eliminate the acid labile groups on the resin in the positive pattern resulting from the previous step, and to induce crosslinking in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition, coating a reversal film-forming composition thereon to form a reversal film, and dissolving away the positive pattern using an alkaline wet etchant.
 26. The process of claim 25 wherein said protective film-forming composition is based on a copolymer comprising amino-containing recurring units.
 27. The process of claim 25 wherein said protective film-forming composition further comprises an amine compound.
 28. The process of claim 1, further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, forming a silicon-containing intermediate film thereon, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a hydrocarbon-based material.
 29. The process of claim 1, further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a silicon-containing material.
 30. The process of claim 1, further comprising the steps of forming a carbon film having a carbon content of at least 75% by weight on the processable substrate, forming an organic antireflection film thereon, and coating a resist composition for positive/negative reversal thereon, the reversal film being formed of a silicon-containing material. 